CN1650450B - Batteries comprising alkali-transition metal phosphates and preferred electrolytes - Google Patents

Batteries comprising alkali-transition metal phosphates and preferred electrolytes Download PDF

Info

Publication number
CN1650450B
CN1650450B CN038100339A CN03810033A CN1650450B CN 1650450 B CN1650450 B CN 1650450B CN 038100339 A CN038100339 A CN 038100339A CN 03810033 A CN03810033 A CN 03810033A CN 1650450 B CN1650450 B CN 1650450B
Authority
CN
China
Prior art keywords
battery
composition
group
constitutes
carbonate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN038100339A
Other languages
Chinese (zh)
Other versions
CN1650450A (en
Inventor
詹姆斯·皮尤
M·耶齐德·赛义迪
海涛·黄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
WILLENS TECHNOLOGIES Inc
Valence Technology Inc
Original Assignee
WILLENS TECHNOLOGIES Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=28673938&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN1650450(B) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by WILLENS TECHNOLOGIES Inc filed Critical WILLENS TECHNOLOGIES Inc
Publication of CN1650450A publication Critical patent/CN1650450A/en
Application granted granted Critical
Publication of CN1650450B publication Critical patent/CN1650450B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

Lithium batteries comprising: (a) an electrode comprising a material of the formula AaMb(XY4)cZd, wherein (i) A is an alkaline metal and 0 < a <= 9; (ii) M comprises a transition metal, and 1 <= B <=3; (III) XY4 is X'O4-XY'X, X'O4-y,Y''2y, X'S4, or mixtures thereof, where X' is P, As, Sb, Si, Ge, V, S, or mixtures thereof; X' is P, As, Sb, Si, Ge, V, or mixtures thereof; Y' is halogen, S, N, or mixtures thereof; 0 <= x < 3; and 0 < y <= 2; and 0 < x <= 3; and (iv) Z is OH, halogen, or mixtures thereof, and 0 <= d <= 6; and (b) a counter-electrode; and (c) an electrolyte comprising an alkyl and/or alkylene carbonate and a cyclic ester. Preferably, M additionally comprises at least one non-transition metal. Preferred embodiments include those having an olivine structure, where c = 1, and those having a NASICON structure, where c=3.

Description

The battery that comprises alkali transition metal phosphate and preferred electrolyte
Technical field
The present invention relates to battery.Especially, the present invention relates to such battery, this battery comprises: active material, and it comprises lithium or otheralkali metal, transition metal and phosphate or proximate composition (moiety); And electrolyte, it comprises alkylene carbonate and cyclic ester.
Background technology
Known in the prior art have diversified electro-chemical cell unit (cell) or " battery (battery) " to be.In general, battery is the device that chemical energy is converted to electric energy by the electrochemical oxidation reduction reaction.Battery is used in extensively various application, and particularly conduct can't be by the power supply of the power-producing device of centrally connected power source (for example utilizing the commercial power plant of common transmission line) in practicality.
Battery generally can be described to comprise three parts: anode, and it contains the material at (promptly in power supply) oxidized (generation electronics) during the battery discharge; Negative electrode, it contains during battery discharge the material that is reduced (accepting electronics); And electrolyte, it is for the migration of ion between anode and negative electrode.At interdischarge interval, anode is the negative pole of battery, and negative electrode then is the positive pole of battery.Battery can more specifically characterize by the concrete material of forming each parts in these three parts.Select these parts to produce to have at application-specific and the optimised specific voltage and the battery of flash-over characteristic.
Battery generally can also be classified as: " primary cell ", electro-chemical reaction are irreversible in fact, thereby battery discharge in a single day just becomes and can not use again; And " secondary cell ", electro-chemical reaction is reversible at least in part, thus battery can " be recharged ", and can repeatedly use.Because secondary cell easy-to-use (particularly be difficult to change in the application of battery), can reduce cost (by reducing the needs of changing) and to environment useful (by reducing refuse), so secondary cell is used more and morely in many application from Battery disposal.
Known in the prior art have various secondary battery systems.Prevailing system is lead-acid, nickel-cadmium, nickel-zinc, Ni-Fe, silver oxide, nickel metal hydride, rechargeable zinc-manganese dioxide, zinc-bromine, metal-air and lithium battery.The system that contains lithium and sodium can provide many potential benefits, because these weight metals are light, has high standard electrode potential simultaneously.For various reasons, lithium battery is commercial particularly tempting, because they have high-energy-density, higher cell voltage and the shelf life of growing (shelf-life).
Lithium battery is to be prepared from by the one or more lithium electrochemical cells that contain electro-chemical activity (electricity activation) material.In such battery, those batteries with lithium metal anode and metal chalcogenide (oxide) negative electrode are commonly referred to as " lithium metal " battery.Electrolyte generally comprises the lithium salts that is dissolved in one or more solvents, and this solvent generally is the thin proton-organic solvent (nonaqueous aprotic organicsolvents) of non-water.Other electrolyte are solid electrolyte (generally being polymeric matrix (matrix)), it contains the ionic conduction medium (generally being the lithium salts that is dissolved in the organic solvent) that combines with polymer phase, this polymer itself can be an ionic conduction, but electric insulation.
Battery unit with lithium metal anode and metal chalcogenide negative electrode is recharged under initial condition.At interdischarge interval, the lithium metal produces electronics at anode to external circuit.Produced the ion of positively charged, they pass electro-chemical activity (electricity activation) material that electrolyte arrives negative electrode.Electronics from anode passes external circuit, to the device power supply, and turns back to negative electrode.
Another lithium battery utilization " embeds anode (insertion anode) " but not the lithium metal, and usually is called " lithium ion " battery.Embedding or " insertion " electrode contain the material with lattice structure, and ion can be embedded in this structure and be extracted subsequently.Do not adopt chemical method to change insert material, these ions can make the internal crystal framework length expansion of compound a little, and key breaks or the atom reorganization and do not have widely.Embed anode and for example contain lithium metal chalcogenide, lithium metal oxide or material with carbon element: such as coke and graphite.These negative poles use with the embedding negative electrode that contains lithium.Under their initial condition, because anode does not contain cationic source, so these battery units are not recharged.Therefore, before using, these battery units must charge, so as with cation (lithium) from the cathodic migration to the anode.At interdischarge interval, lithium turns back to negative electrode from the anode migration then.During follow-up recharging, lithium turns back to the anode that it embeds again from cathodic migration once more.Lithium ion (Li during charging and discharge cycles +) between anode and negative electrode this back and forth the migration cause these battery units to be called as " rocking chair (rocking chair) " battery.
Various materials have been proposed as the active material of cathode in the lithium battery.These materials comprise for example MoS 2, MnO 2, TiS 2, NbSe 3, LiCoO 2, LiNiO 2, LiMn 2O 4, V 6O 13, V 2O 5, SO 2, CuCl 2Transition metal oxide is Li such as general formula xM 2O yMetal oxide, be that these have institute's preferable material in the battery of intercalation electrode.Other materials comprises phosphoric acid transition metal lithium, such as LiFePO 4And Li 3V 2(PO 4) 3These materials that have analog structure with olivine or NASICON (sodium superionic conductors) material are known in those skilled in the art.Active material of cathode known in those skilled in the art is disclosed in the following document: S.Hossain, " rechargeable lithium battery (ambient temperature) " (" Rechargeable Lithium Batteries (Ambient Temperature) "), handbook of batteries (Handbook of Batteries), second edition (2d ed.), the 36th chapter, Mc-Graw Hill (1995); The distribution on March 18th, 4,194,062,1980 of people's such as Carides United States Patent (USP); The distribution on August 7th, 4,464,447,1984 of people's such as Lazzari United States Patent (USP); The distribution on July 2nd, 5,028,500,1991 of people's such as Fong United States Patent (USP); The distribution on July 14th, 5,130,211,1992 of people's such as Wilkinson United States Patent (USP); People's such as Koksbang United States Patent (USP) 5,418,090, distribution on May 23 nineteen ninety-five; The distribution on May 7th, 5,514,490,1996 of people's such as Chen United States Patent (USP); The distribution on July 23rd, 5,538,814,1996 of people's such as Kamauchi United States Patent (USP); The distribution on December 9th, 5,695,893,1997 of people's such as Arai United States Patent (USP); The distribution on September 8th, 5,804,335,1998 of people's such as Kamauchi United States Patent (USP); The distribution on February 16th, 5,871,866,1999 of people's such as Barker United States Patent (USP); The distribution on June 8th, 5,910,382,1999 of people's such as Goodenough United States Patent (USP); People's such as Barker PCT publication number WO/00/31812, on June 2nd, 2000 is open; The PCT publication number WO/00/57505 of Barker, on September 28th, 2000 is open; The distribution in October 24 in 6,136,472,2000 year of people's such as Barker United States Patent (USP); The distribution on November 28th, 6,153,333,2000 of the United States Patent (USP) of Barker; People's such as Ravet European Patent Publication No is open on November 2nd, 1,049,182,2000; The PCT publication number WO/01/13443 of Barker, February 22 calendar year 2001 is open; People's such as Barker PCT publication number WO/01/54212, July 26 calendar year 2001 is open; People's such as Barker PCT publication number WO/01/84655, November 8 calendar year 2001 is open.
Preferably, this cathode material shows the high free energy with the lithium reaction, can discharge and embed a large amount of lithiums, when embedding and extract lithium, keep its lattice structure, allow the rapid diffusion of lithium, satisfactory electrical conductivity is provided, can be dissolved in large quantities in the electrolyte system of battery, and be easy to and production economically.Yet many cathode materials well known in the art lack one or these multinomial characteristics.As a result, for example many these materials undertension that can't produce economically, provide, charging capacity deficiency or repeatedly losing the ability that recharges after the circulation.
Summary of the invention
The invention provides the battery that comprises active material, this active material comprises lithium or otheralkali metal, transition metal and optionally other metals and phosphate, replacement phosphate (substituted phosphate) or proximate composition.Especially, the invention provides a kind of lithium battery, comprising:
(a) first electrode comprises that molecular formula is A aM b(XY 4) cZ dActive material, wherein
(i) A is selected from the group that Li, Na, K and composition thereof constitute, and 0＜a≤9;
(ii) M is one or more metals, comprises at least a metal that can be oxidized to higher valence state, and 1≤b≤3;
(iii) XY 4Be selected from X ' O 4-xY ' x, X ' O 4-yY ' 2y, X " S 4, and composition thereof the group that constitutes, wherein X ' be selected from P, As, Sb, Si, Ge, V, S, and composition thereof the group that constitutes; X " be selected from P, As, Sb, Si, Ge, V, and composition thereof the group that constitutes; Y ' be selected from halogen, S, N, and composition thereof the group that constitutes; 0≤x＜3; 0＜y≤2; 0＜c≤3;
(iv) Z is OH, halogen or its mixture, and 0≤d≤6; And
Wherein M, XY 4, Z, a, b, c, d, x and y selected like this, promptly keeps the electric neutrality of described compound;
(b) second electrode, it is the counterelectrode (counter-electrode) of described first electrode; And
(c) electrolyte comprises the mixture of cyclic ester and carbonic ester (carbonate), and this carbonic ester is selected from the group that is made of alkyl carbonate, alkylene carbonate and composition thereof.
In a preferred embodiment, M comprises two or more transition metal in the 4th to 11 family of periodic table.In another preferred embodiment, M comprises M ' M ", wherein M ' is at least a transition metal in the 4th to 11 family of periodic table; M " be at least a element in the 2nd, 3 and 12 to 16 families of periodic table.Preferred embodiment comprises these situations: c=1, c=2 and c=1.Preferred embodiment comprises these situations: a≤1 and c=1; A=2 and c=1; And a≤3 and c=3.Preferred embodiment also comprises the material (here be called " olivine material (olivines) ") of those similar in mineral olivine, and those similar are in NASICON (NA Super Ionic CONductor; The sodium superionic conductors) material (being called " sodium superionic conductors material (NASICONs) " here).In particularly preferred embodiment, M comprises Co eFe fM 1 gM 2 hM 3 i, M wherein 1It is at least a transition metal in the 4th to 11 family of periodic table; M 2Comprise one or more+2 oxidation state nontransition metal; M 3Comprise one or more+3 oxidation state nontransition metal, and e+f+g=b.In such embodiments, preferably, A comprises Li, 0.8≤a≤1.2,0.8≤b≤1.5, c=1.As used herein, unless otherwise specified, be described as equaling ("="), be less than or equal to ("≤") or be intended to comprise and approximate or functionality ground is equivalent to the scope of the value of described number more than or equal to variable of (" 〉=") certain number by algebraic approach.
Have been found that new battery of the present invention compares with device with these materials known in those skilled in the art and have many benefits.These benefits comprise that capacity increases, circulation ability strengthens, invertibity strengthens and cost in reducing or multinomial.Concrete benefit of the present invention and embodiment become obvious here from the specific descriptions of setting forth.Yet, should be appreciated that specific descriptions and instantiation in some embodiment, only are intended to be explanation in the expression preferred embodiment, be not to be intended to limit the scope of the invention.
Embodiment
The invention provides and contain special electrodes active material and electrolytical battery.Here used " battery " is meant a kind of device that is used to produce electric one or more electro-chemical cells unit that comprises.Each electro-chemical cell unit comprises anode, negative electrode and electrolyte.Two or more electro-chemical cells unit can be combined or " piling up ", has the battery of many battery units of a voltage with foundation, and this voltage is the voltage sum of each battery unit.
Electrode active material of the present invention can be used for anode, negative electrode or both.Preferably, active material of the present invention is used in the negative electrode.(used here " anode " and " negative electrode " are meant the electrode that oxidation and reduction take place respectively during battery discharge.During battery charge, the position opposite of oxidation and reduction.Simultaneously, word here " preferably " and " preferably " are meant embodiments of the invention, and they provide specific benefit under particular environment.Yet other embodiment also can be preferred under identical or other environment.In addition, to the narration of one or more preferred embodiments and do not mean that other embodiment are useless, be not intended to from scope of the present invention, get rid of other embodiment) yet.
Electrode active material:
The invention provides the active material (being called " electrode active material " here) that comprises lithium or otheralkali metal, transition metal, phosphate or proximate composition and (optional) halogen or hydroxyl (hydroxyl moiety).These electrode active materials comprise that molecular formula is A aM b(XY 4) cZ dMaterial.(word here " comprises " and other similar term, be intended to nonrestrictive, thereby other similar items are not got rid of in the narration of the project in the tabulation, these similar items also are useful in material of the present invention, compound, apparatus and method).
A be selected from by Li (lithium), Na (sodium), K (potassium), and composition thereof the group that constitutes.In a preferred embodiment, A is the mixture of mixture, Li and K of Li, Li and Na or the mixture of Li, Na and K.In another preferred embodiment, A is the mixture of Na or Na and K.Preferably, " a " is from about 0.1 to about 6, more preferably from about 0.2 to about 6.When c=1, a is preferably from about 0.1 to about 3, and preferably from about 0.2 to about 2.In a preferred embodiment, when c=1, a is approximately less than 1.In another preferred embodiment, when c=1, a is about 2.Preferably, " a " is from about 0.8 to about 1.2.When c=2, a is preferably from about 0.1 to about 6, preferably from about 1 to about 6.When c=3, a is preferably from about 0.1 to about 6, preferably from about 2 to about 6, and preferably from about 3 to about 6.In another embodiment, " a " preferably from about 0.2 to about 1.0.
In a preferred embodiment, from electrode active material, remove the variation that alkali metal can be attended by the oxidation state of at least a metal in the metal that comprises M.In electrode active material, the quantity that can be used for the described metal of oxidation has determined can removed alkali-metal quantity.In general the application, these notions are well known in the prior art, and for example are disclosed in the United States Patent (USP) distribution on October 16th, 4,477,541,1984 of Fraioli; And people's such as Barker United States Patent (USP) distribution on October 24th, 6,136,472,2000, here the two all is incorporated herein by reference.
With reference to general formula A aM b(XY 4) cZ d, wherein as quantity b ' and the valence state V of oxidizable metal M MFunction, can removed alkali-metal quantity a ' be:
a’＝b’(ΔV M)，
Δ V wherein MBe poor (term " oxidation state " and " valence state " can alternatively be used mutually in the prior art) of the valence state that is easy to get of metal valence state in the active material and this metal.For example, for comprising+active material of iron (Fe) under 2 oxidation state Δ V M=1, wherein iron can be oxidized to+3 oxidation state (although iron also can be oxidized under some environment+4 oxidation state).If b=1 (Fe of an atomic unit in the material of every atomic unit), then the maximum quantity a ' that battery cycle period can removed alkali metal (oxidation state+1) is 1 (alkali metal of an atomic unit).If b=1.25, then battery cycle period can removed alkali-metal maximum quantity a ' be 1.25.
In general, " a " value in the active material can change in the scope widely.In a preferred embodiment, active material is synthesized the lithium ion battery that is used for preparing discharge condition.These active materials are characterised in that: high relatively " a " value, the corresponding low-oxidation-state of the M of active material.When battery when initially electriferous state is not recharged from it, the lithium of quantity a ' is removed from active material as mentioned above.Value that resulting structures is characterised in that low " a " keeps original " b " value simultaneously in essence, and this structure contains lithium and transition metal, and this lithium is than still less (being a-a ') in the preparation state, and this transition metal is in than oxidation state higher in the preparation state.Active material of the present invention comprises the following material of nascent state (that is, with produced the same) and forms during battery operated before being contained in electrode material (that is, by embedding or removal Li or otheralkali metal).
Value in the active material " b " and total chemical valence M should be such, and the gained active material is electroneutral (that is, the positive charge of all cationic species equals the negative electrical charge of all anionic species in the material), as hereinafter further as described in.Have complex element (M1, the clean chemical valence V of M M2......Mt) MCan represent by following molecular formula:
V M＝V M1b 1+V M2b 2+......V Mtb t
B wherein 1+ b 2+ ... b t=1, and V M1Be the oxidation state of M1, V M2Be the oxidation state of M2, or the like (will be further described below the M of electrode active material and the clean chemical valence of other compositions).
M is one or more metals, and it comprises at least aly can be oxidized to higher valence state (Co for example + 2→ Co + 3) metal, be preferably from the 4-11 family (group) of periodic table the transition metal of selecting.Here mentioned " family " is meant defined periodic table family's sequence number (being the hurdle) in the current I UPAC periodic table.For example, be incorporated herein by reference referring to the people's such as Barker that issued on October 24th, 2000 United States Patent (USP) 6,136,472.In another preferred embodiment, M also comprise be selected from periodic table the 2nd, 3, the nontransition metal in the 12-16 family.
In another preferred embodiment, preferably, when c=1, M comprises Co eFe fM 1 gM 2 hM 3 i, M wherein 1Be at least a transition metal in the 4th to 11 family, M 2Be at least a+2 oxidation state nontransition metal, M 3Be at least a+3 oxidation state nontransition metal, e 〉=0, f 〉=0, g 〉=0, h 〉=0, i 〉=0, and e+f+g+h+i=b.Preferably, among e and the f one of them more preferably is all greater than zero greater than zero at least.In a preferred embodiment, 0＜e+f+g+h+i≤2, more preferably, 0.8≤e+f+g≤1.2, and even more preferably, 0.9≤e+f+g≤1.0.Preferably, e 〉=0.5, more preferably, e 〉=0.8.Preferably, 0.01≤f≤0.5, more preferably, 0.05≤f≤0.15.Preferably, 0.01≤g≤0.5, more preferably, 0.05≤g≤0.2.In a preferred embodiment, h+i＞1, preferably, 0.01≤h+i≤0.5, and even more preferably, 0.01≤h+i≤0.1.Preferably, 0.01≤h≤0.2, more preferably, 0.01≤h≤0.1.Preferably, 0.01≤i≤0.2, more preferably 0.01≤i≤0.1.
Here useful transition metal comprise from Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zr (zirconium), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Cd (cadmium), Hf (hafnium), Ta (tantalum), W (tungsten), Re (rhenium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Hg (mercury), and composition thereof the metal selected the group that constitutes.Preferably be selected from the first row transition series (period 4 of periodic table) in the combination that Ti, V, Cr, Mn, Fe, Co, Ni, Cu and composition thereof constitute.Particularly preferred transition metal comprise be selected from Fe, Co, Ti, Mn, and composition thereof the group that constitutes.In a preferred embodiment, M is Co 1-mFe m, 0＜m≤0.5 wherein, preferred 0＜m≤0.2.Although there is multiple oxidation state in these transition metal, in certain embodiments, most preferably transition metal has the a+2 oxidation state.Here the used narration of kind (can therefrom select single composition or mixture of ingredients) to element, material or other compositions is intended to comprise that the institute of the composition that lists might subclass make up and composition thereof.
In a preferred embodiment, M also comprises one or more nontransition metal.Here " nontransition metal " of indication comprise periodic table the 2nd, 3, in the 12-16 family, can form the stabilizing active material and can not hinder greatly in normal working conditions and embed or remove the metal of lithium or otheralkali metal and nonmetal from active material.Preferably, these elements do not comprise C (carbon), Si (silicon), N (nitrogen) and P (phosphorus).Preferred nontransition metal comprises that those are not easy to be oxidized to the metal of the higher valence state in the electrode active material in normal working conditions.Here useful nontransition metal is selected from the group that is made of following element: the 2nd family's element, preferred Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium); The 3rd family's element, preferred Sc (scandium), Y (yttrium); And lanthanide series, preferred La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium); The 12nd family's element, preferred Zn (zinc) and Cd (cadmium); The 13rd family's element, preferred B (boron), Al (aluminium), Ga (gallium), In (indium), Tl (thallium); The 14th family's element, preferred Si (silicon), Ge (germanium), Sn (tin), Pb (lead); The 15th family's element, preferred As (arsenic), Sb (antimony), Bi (bismuth); The 16th family's element, preferred Te (tellurium); And composition thereof.Preferred nontransition metal comprises the 2nd family's element, the 12nd family's element, the 13rd family's element, the 14th family's element.Particularly preferred nontransition metal comprise be selected from Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and composition thereof the group that constitutes.Particularly preferably be selected from Mg, Ca, Zn, Ba, Al, and composition thereof the nontransition metal in the group that constitutes.
As described further herein, " b " selected like this, promptly keeps the electric neutrality of electrode active material.In a preferred embodiment, when c=1, b is from about 1 to about 2, is preferably about 1.In another preferred embodiment, when c=2, b is from about 2 to about 3, is preferably about 2.
XY 4Be anion, preferably be selected from X ' O 4-xY ' x, X ' O 4-yY ' 2y, X " S 4And composition thereof the group that constitutes, wherein X ' be selected from P (phosphorus), As (arsenic), Sb (antimony), Si (silicon), Ge (germanium), V (vanadium), S (sulphur), and composition thereof the group that constitutes; X " be selected from P, As, Sb, Si, Ge, V, and composition thereof the combination that constitutes.Here useful XY 4Anion comprise phosphate radical, silicate, germanic acid root, vanadic acid root, arsenate, metaantimmonic acid root, its sulfur-bearing congener (sulfur analogs thereof), and composition thereof.In a preferred embodiment, X ' and X " all be selected from the group that P, Si and composition thereof constitute.In particularly preferred embodiment, X ' and X " be P.
Y ' is selected from the group that halogen, S, N and composition thereof constitute.Preferably, Y ' is F (fluorine).In a preferred embodiment, 0≤x≤3; And 0＜y≤2, thereby XY 4Oxygen (O) part in the component (moiety) can be substituted by halogen.In another preferred embodiment, x and y are 0.In particularly preferred embodiment, XY 4Be X ' O 4, wherein X ' is preferably P or Si, more preferably P.In another special preferred embodiment, XY 4Be PO 4-xY ' X, wherein Y ' is a halogen, and 0＜x≤1.Preferably, 0.01≤x≤0.05, more preferably, 0.02≤x≤0.03.
In a preferred embodiment, XY 4Be PO 4(phosphate radical) or PO 4With another XY 4The mixture (that is, when X ' was not P, Y ' was not O, and perhaps the two is not, defines as the front) of group.When the part phosphate radical was substituted, preferably, substituting group (substitute group) existed with seldom quantity for phosphate radical.In a preferred embodiment, XY 4Comprise 80% or one or more phosphate radical substituents of more phosphate radical and about at the most 20%.The phosphate radical substituent comprise without restriction silicate, sulfate radical, metaantimmonic acid root, germanic acid root, arsenate, a fluorine one phosphate radical (monofluoromonophosphate), difluoro one phosphate radical (difluoromonophosphate), its sulfur-bearing congener, and composition thereof.Preferably, XY 4Comprise one or more phosphate radical substituents (this percentage is based on molar percentage) of about 10% at most.Preferred XY 4Group comprises those molecular formula (PO 4) 1-k(B) kGroup, wherein B represents XY 4XY outside group or the phosphate radical 4The combination of group, and k≤0.5.Preferably, k≤0.8, more preferably, k≤0.2, more preferably k≤0.1.
Z is OH, halogen or its mixture.In a preferred embodiment, Z be selected from OH (hydroxyl), F (fluorine), Cl (chlorine), Br (bromine), and composition thereof the group that constitutes.In a preferred embodiment, Z is OH.In another preferred embodiment, Z is the mixture of F or F and OH, Cl or bromine.In a preferred embodiment, d=0.In another preferred embodiment, d＞0, preferably from about 0.1 to about 6, more preferably, from about 0.2 to about 6.In these embodiments, when c=1, d is preferably from about 0.1 to about 3, and preferably from about 0.2 to about 2.In a preferred embodiment, when c=1, d is approximately 1.When c=2, d is preferably from about 0.1 to about 6, and preferably from about 1 to about 6.When c=3, d is preferably from about 0.1 to about 6, preferably, from about 2 to about 6, preferably from about 3 to about 6.
M, XY 4, the composition of Z and the value of a, b, c, d, x and y selected like this, promptly keeps the electric neutrality of electrode active material.Here " electric neutrality " of indication is the state of electrode active material, and wherein, the positively charged species in the material (for example A and M) sum equals the (XY for example of electronegative species in the material 4) sum.Preferably, XY 4Component is constituted as the anion as the unit component, and it is according to X ', X ", the selection of Y ', X and Y has-2 ,-3 or-4 electric charge.Work as XY 4When being the mixture such as preferably phosphoric acid root/phosphate radical substituent etc. as mentioned above, can be according to single XY in the mixture 4Electric charge and composition, make XY 4The net charge of anion is got non integer value.
Generally speaking, the valence state of each composition element of electrode active material can be determined with reference to the composition and the valence state of other composition elements in the material.By reference general formula A aM b(XY 4) cZ d, the electric neutrality of material can utilize following formula to determine:
(V A)a+(V M)b+(V X)c＝(V Y)4c+(V Z)d
V wherein ABe the clean chemical valence of A, V MBe the clean chemical valence of M, V YBe the clean chemical valence of Y, V ZIt is the clean chemical valence of Z.Here the composition of indication " clean chemical valence " is: (a) have the valence state of the composition of individual element, this element appears in the active material with single valence; The perhaps mole weighted sum of the valence state of all elements in (b) constituent element, this constituent element comprises a plurality of elements or comprises the individual element with a plurality of valence states.The clean chemical valence of each composition is represented in following formula:
(V A)b＝[(V A1)a 1+(Val A2)a 2+...(V An)a n]/n；a 1+a 2+...a n＝a
(V M)b＝[(V M1)b 1+(V M2)b 2+...(V Mn)b n]/n；b 1+b 2+...b n＝b
(V X)c＝[(V X1)c 1+(V X2)c 2+...(V Xn)c n]/n；c 1+c 2+...c n＝c
(V Y)c＝[(V Y1)c 1+(V Y2)c 2+...(V Yn)c n]/n；c 1+c 2+...c n＝c
(V Z)d＝[(V Z1)d1+(V Z2)d 2+...(V Zn)d n]/n；d 1+d 2+...d n＝d
Generally speaking, the quantity of M and constituent element are selected by the chemical valence of given X, the value of " c " and the quantity of A, as long as M comprises at least a metal that can oxidation.Valent calculating of M can be simplified as follows, wherein V A=1, V Z=1:
Compound for c=1: (V M) b=(V Y) 4+d-a-(V X)
Compound for c=3: (V M) b=(V Y) 12+d-a-(V X) 3
The value of a, b, c, d, x and y can cause the stoichiometry (stoichiometric) or non-stoichiometry (non-stoichiometric) molecular formula of electrode active material.In a preferred embodiment, the value of a, b, c, d, x and y all is an integer value, obtains the stoichiometry molecular formula.In another preferred embodiment, one or more values has non integer value among a, b, c, d, x and the y.Yet, can understand, have lattice structure (the non-stoichiometry molecular formula A that comprises a plurality of units aM b(XY 4) cZ d) embodiment in, when considering a plurality of unit, this molecular formula can be stoichiometric.That is to say, the unit formula formula when one or more values are non-integer among a, b, c, d, x and the y, the value of each variable becomes an integer value for many units, and this integer value is the least common multiple of each a, b, c, d, x and y.For example, active material Li 2Fe 0.5Mg 0.5PO 4F is non-stoichiometric.Yet for the material that comprises two such units in lattice structure, molecular formula is Li 4FeMg (PO 4) 2F 2
Preferred electrode active material embodiment comprises the compound of following molecular formula:
Li aM b(PO 4) Z d, wherein
(a)0.1＜a≤4；
(b) M is M ' 1-mM " m, wherein M ' is at least a transition metal in the 4th to 11 family of periodic table; M " be periodic table the 2nd, 3, at least a transition metal in the 12-16 family, and 0＜m＜1, and 1≤b≤3; And
(c) Z comprises halogen, and 0≤d≤4; And
Wherein M, Z, a, b and d are selected like this, promptly keep the electric neutrality of described compound.Preferably, M ' be selected from Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and composition thereof the group that constitutes; More preferably, M ' be selected from Fe, Co, Mn, Cu, V, Cr, and composition thereof the group that constitutes.Preferably, M " be selected from Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and composition thereof the group that constitutes; M " be selected from Mg, Ca, Zn, Ba, Al, and composition thereof the group that constitutes.Preferably, Z comprises F.
Another preferred embodiment comprises the compound of following molecular formula:
A aM b(XY 4) 3Z d, wherein
(a) A be selected from Li, Na, K, and composition thereof the group that constitutes, and 2≤a≤9;
(b) M comprises one or more metals, comprises at least a metal that can be oxidized to higher valence state, and 1≤b≤3;
(c) XY 4Be selected from X ' O 4-xY ' x, X ' O 4-yY ' 2y, X " S 4, and composition thereof the group that constitutes, wherein X ' be selected from P, As, Sb, Si, Ge, V, S, and composition thereof the group that constitutes; X " be selected from P, As, Sb, Si, Ge, V, and composition thereof the group that constitutes; Y ' be selected from halogen, S, N, and composition thereof the group that constitutes; 0≤x＜3,0＜y＜4; And
(d) Z is OH, halogen or its mixture, and 0≤d≤6; And
Wherein M, XY 4, Z, a, b, d, x and y selected like this, promptly keeps the electric neutrality of described compound.In a preferred embodiment, A comprises the mixture of Li or Li and Na or K.In another preferred embodiment, A comprises Na, K or its mixture.In a preferred embodiment, M comprises two or more transition metal in the 4th to 11 family of periodic table, be preferably from Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and composition thereof the transition metal selected the group that constitutes.In another preferred embodiment, M comprises M ' 1-mM " m, wherein M ' is at least a transition metal in the 4th to 11 family of periodic table, and M " be periodic table the 2nd, 3, at least a element in the 12-16 family, and 0＜m＜1.Preferably, M ' be selected from Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and composition thereof the group that constitutes; More preferably, M ' be selected from Fe, Co, Mn, Cu, V, Cr, and composition thereof the group that constitutes.Preferably, M " be selected from Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and composition thereof the group that constitutes; More preferably, M " be selected from Mg, Ca, Zn, Ba, Al, and composition thereof the group that constitutes.In a preferred embodiment, XY 4Be PO 4In another preferred embodiment, X ' comprise As, Sb, Si, Ge, S, and composition thereof; X " comprise As, Sb, Si, Ge, and composition thereof, and 0＜x＜3.In a preferred embodiment, Z comprises mixture or its mixture of F or F and Cl, Br, OH.In a preferred embodiment, Z comprises the mixture of OH or itself and Cl or Br.
Another preferred embodiment comprises the compound of following molecular formula:
A aM 1 eM 2 fM 3 gXY 4, wherein
(a) A be selected from Li, Na, K, and composition thereof the group that constitutes, and 0＜a≤2;
(b) M 1Comprise one or more transition metal, wherein e＞0;
(c) M 2Comprise one or more+2 oxidation state nontransition metal, wherein f＞0;
(d) M 3Comprise one or more+3 oxidation state nontransition metal, wherein g＞0; And
(e) XY 4Be selected from X ' O 4-xY ' x, X ' O 4-yY ' 2y, X " S 4, and composition thereof the group that constitutes, wherein X ' be selected from P, As, Sb, Si, Ge, V, S, and composition thereof the group that constitutes; X " be selected from P, As, Sb, Si, Ge, V, and composition thereof the group that constitutes; Y ' be selected from halogen, S, N, and composition thereof the group that constitutes; And 0≤x≤3,0＜y≤2; And
Wherein e+f+g＜2, and selection M 1, M 2, M 3, XY 4, a, e, f, g, x and y, to keep the electric neutrality of described compound.At XY 4Be PO 4-xY ' xAnd M 1Be among the embodiment of a+2 oxidation state transition metal, a+2e+2f+3g=3-x.
Preferably, e+f+g=b.In a preferred embodiment, 0＜e+f+g＜2, more preferably, 0.8≤e+f+g＜1.5, and even more preferably, 0.9≤e+f+g≤1,0.01≤f+g≤0.5 wherein, more preferably, 0.05≤f+g≤0.2, and even more preferably, 0.05≤f+g≤0.1.
In a preferred embodiment, A is Li.Preferably, M 1It is at least a transition metal in the 4th to 11 family of periodic table; M 2Be periodic table the 2nd, 3, at least one nontransition metal among the 12-16, M 3It is the a+3 oxidation state metal that is selected from the 13rd family.Preferably, M 1Be selected from Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and composition thereof the group that constitutes; More preferably, M 1Be be selected from Fe, Co, Mn, Cu, V, Cr, and composition thereof the a+2 oxidation state transition metal in the group that constitutes.Preferably, M 2Be selected from+group that 2 oxidation state nontransition metal and composition thereof constitute; More preferably, M 2Be selected from Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Hg, and composition thereof the group that constitutes.Preferably, M 3Be a+3 oxidation state nontransition metal, preferably, M 3Be selected from the 13rd family, more preferably, be selected from Sc, Y, La, Ac, B, Al, Ga, In, Tl, and composition thereof.Preferably, M 3Be Al.Preferably, 0＜f+g＜1, preferably, 0.01≤f+g≤0.3, more preferably, 0.05≤f+g≤0.1.Preferably, 0.01≤f≤0.3, more preferably, 0.05≤f≤0.1, even more preferably, 0.01≤f≤0.03.Also preferably, 0.01≤g≤0.3, more preferably, 0.05≤g≤0.1, even more preferably, 0.01≤g≤0.03.
Another preferred embodiment comprises the compound of following molecular formula:
Li aCo eFe fM 1 gM 2 hM 3 iXY 4, wherein
(a) 0＜a≤2, e＞0, and f＞0;
(b) M 1Be one or more transition metal, g 〉=0 wherein;
(c) M 2Be one or more+2 oxidation state nontransition metal, wherein h 〉=0;
(d) M 3Be one or more+3 oxidation state nontransition metal, wherein i 〉=0; And
(e) XY 4Be selected from X ' O 4-xY ' x, X ' O 4-yY ' 2y, X " S 4, and composition thereof the group that constitutes, wherein X ' be selected from P, As, Sb, Si, Ge, V, S, and composition thereof the group that constitutes; X " be selected from P, As, Sb, Si, Ge, V, and composition thereof the group that constitutes; Y ' be selected from halogen, S, N, and composition thereof the group that constitutes; 0≤x≤3,0＜y≤2;
Wherein e+f+g+h+i≤2, and selection M 1, M 2, M 3, XY 4, a, e, f, g, h, i, x and y, to keep the electric neutrality of described compound.Preferably, 0.8≤e+f+g+h+i≤1.2, more effectively, 0.9≤e+f+g+h+i≤1.Preferably, e 〉=0.5, more preferably, e 〉=0.8.Preferably, 0.01≤f≤0.5, more preferably, 0.05≤f≤0.15.Preferably, 0.01≤g≤0.5, more preferably, 0.05≤g≤0.2.Preferably, M 1Be selected from Ti, V, Cr, Mn, Ni, Cu, and composition thereof the group that constitutes.Preferably, M 1Be selected from Mn, Ti, and composition thereof the group that constitutes.
Preferably, h+i＞0, more preferably, 0.01≤h+i≤0.5, more preferably, 0.02≤h+i≤0.3.Preferably, 0.01≤h≤0.2, more preferably, 0.01≤h≤0.1.Preferably, M 2Be selected from Be, Mg, Ca, Sr, Ba, and composition thereof the group that constitutes.More preferably, M 2Be Mg.Preferably, 0.01≤i≤0.2, more preferably, 0.01≤i≤0.1.Preferably, M 3Be selected from B, Al, Ga, In, and composition thereof the group that constitutes.More preferably, M 3Be Al.
In one embodiment, XY 4Be PO 4In another embodiment, XY 4Be PO 4-xF x, and 0＜x≤1, preferably, 0.01≤x≤0.05.
Another embodiment comprises the compound with olivine structural.At the charging and the interdischarge interval of battery, lithium ion is added to active material and is removed from active material, and preferably, substantial variations does not take place the crystal structure of material.Such material has alkali metal (for example lithium), transition metal (M) and XY 4The position of (for example phosphate radical) component.In certain embodiments, all positions of crystal structure are all occupied.In other embodiments, some positions are idle, and this depends on for example state of oxidation of metal (M).These preferred compounds are compounds of following molecular formula:
LiM(PO 4-xY’ x)
Wherein M is M 1 gM 2 hM 3 iM 4 j, and
(a) M 1Be one or more transition metal;
(b) M 2Be one or more+2 oxidation state nontransition metal;
(c) M 3Be one or more+3 oxidation state nontransition metal;
(d) M 4Be one or more+1 oxidation state nontransition metal; And
(e) Y ' is a halogen; And
G＞0; H 〉=0; I 〉=0; J 〉=0; G+h+i+j≤1; And the clean chemical valence of M is 2-x.Preferably, g 〉=0.8, more preferably, g 〉=0.9.Preferably, M 1Be be selected from V, Cr, Mn, Fe, Co, Ni, and composition thereof the a+2 oxidation state nontransition metal in the group that constitutes.More preferably, M 1Be be selected from Fe, Co, and composition thereof the group that constitutes.Preferably, M 1Also comprise Ti.
Preferably, h+i＞0.1, more preferably, 0.02≤h+i≤0.5, more preferably, 0.02≤h+i≤0.3.Preferably, 0.01≤h≤0.2, more preferably, 0.01≤h≤0.1.Preferably, M 2Be selected from Be, Mg, Ca, Sr, Ba, and composition thereof the group that constitutes.Preferably, 0.01≤i≤0.2, more preferably, 0.01≤i≤0.1.Preferably, M 3Be Al.
In one embodiment, j=0.In another embodiment, 0.01≤j≤0.1.Preferably, M 4Be selected from the group that Li, Na and K constitute.More preferably, M 4Be Li.
In a preferred embodiment, x=0.In another embodiment, 0＜x≤1.In this embodiment, preferably, 0.01≤x≤0.05, and g+h+i+j≤1.In an embodiment, when j=0, preferably, g+h+i=1-x.
Preferred active material comprises LiFePO 4, LiFe 0.9Mg 0.1PO 4, LiFe 0.8Mg 0.2PO 4, Li 1.025Co 0.85Fe 0.05Al 0.025Mg 0.05PO 4, Li 1.025Co 0.80Fe 0.10Al 0.025Mg 0.05PO 4, Li 1.025Co 0.75Fe 0.15Al 0.025Mg 0.05PO 4, Li 1.025Co 0.7(Fe 0.4Mn 0.6) 0.2Al 0.025Mg 0.05PO 4, LiCo 0.8Fe 0.1Al 0.025Ca 0.05PO 3.975F 0.025, LiCo 0.8Fe 0.1Al 0.025Mg 0.05PO 3.975F 0.025, LiCo 0.8Fe 0.1Ti 0.025Mg 0.05PO 4, Li 1.025Co 0.8Fe 0.1Ti 0.025Al 0.025PO 4, Li 1.025Co 0.8Fe 0.1Ti 0.025Mg 0.025PO 3.975F 0.025, LiCo 0.825Fe 0.1Ti 0.025Mg 0.025PO 4, LiCo 0.85Fe 0.075Ti 0.025Mg 0.025PO 4, and composition thereof.Particularly preferred active material is LiCo 0.8Fe 0.1Al 0.025Mg 0.05PO 3.975F 0.025
Manufacture method:
General formula is A aM b(XY 4) cZ dActive material can be by original material is reacted under solid-state reaction easily synthetic, include or do not comprise the oxidation or the reduction of metal species simultaneously.Consider institute's active material again, according to the desired value of a in the product, b, c and d, parent material is selected as containing from " a " mol alkali metal A in institute's active material, from " b " mole metal M in institute's active material, from " c " mole of phosphoric acid root (or other XY4 species) in institute's active material and " d " mole halide or hydroxide Z.As described below, specific original material can be a plurality of composition A, M, XY 4Or the source material of Z.Alternatively, can react with one or more excessive original materials.At this moment, the stoichiometry of product will be by composition A, M, XY 4Or the reagent of limiting the quantity of among the Z (limiting reagent) is determined.Because at this moment at least some original materials will appear in the mixture of reaction products, so always be desirable to provide all original materials of definite mole.
In a scheme, the component XY of active material 4Comprise X ' O 4-xY ' xRepresented substituting group, wherein x is less than or equal to 1, and preferably is less than or equal to about 0.1.These substituting groups can synthesize by original material is provided, and these original materials also comprise phosphate or other X ' O of certain molar weight except that comprising alkali metal and other metals 4Material, this mole equal production and contain X ' O 4The required quantity of product.When Y ' was F, original material also comprised the fluoride source of enough moles, and this mole is enough to replace the F in the product shown in the molecular formula.This is usually by comprising in original material that at least " x " mole F realizes.For the embodiment of d＞0, fluoride source uses with the mole limit amount, so that fluoride is incorporated the component as Z-into.The source of F comprises contains fluorine ion (F -) or hydrogen difluoride ion (HF 2 -) ionic compound.Cation can be any cation that forms stable compound with fluorine ion or hydrogen difluoride ion anion.Example comprises+1 ,+2 and+3 metal cations, and ammonium and other cationic nitrogenous.Ammonium is a preferred cation, because it is easy to form volatile byproducts, these accessory substances are removed from reactant mixture easily.
Similarly, in order to make X ' O 4-xN x, the original material that contains " x " mole of nitrogen ion (nitride ion) source will be provided.The nitride source is known for those skilled in the art, comprises such as Li 3N and (NH 4) 3Nitridation salts such as N.
Preferably, form, utilize the original material of stoichiometric to synthesize active material of the present invention based on the expection of the represented product of top subscript a, b, c and d.Alternatively, can utilize excessive stoichiometric one or more original materials to carry out this reaction.At this moment, the stoichiometry of product will be determined by the reagent of limiting the quantity of in the composition.In mixture of reaction products, also have at least some unreacted original materials.Because these impurity in the active material normally unwanted (the reduction carbon that removes as hereinafter discuss) are so generally preferably provide all original materials of relatively accurate mole.
Be heated certain hour and in the following time of temperature that is enough to the realization response product, composition A, M, phosphate radical (or other XY 4Component) the optional source of source, above-mentioned F or N, the optional source of Z can solid-state next react.Original material provides with powder or particulate form.These powder can utilize any technology in the kinds of processes to be mixed together, for example by ball milling, in mortar and pestle, mix etc.Subsequently, the compound of Powdered original material can be pressed into bead and/or form with jointing material, but to form the reactant mixture of close adhesion.This reactant mixture generally is heated in stove under about 400 ℃ or higher temperature, forms until product.
The another way that is used for carrying out this reaction under low temperature more is the hydrothermal solution method.In the hydrothermal solution reaction, original material mixes such as water with small amount of liquid, and is placed in the pressurized tank (bomb).This reaction temperature is restricted to can be by adding the temperature of depressing heating fluid attitude water and used particular reactor ware and can reaching.
This reaction can need not redox to be carried out, and perhaps, if desired, can carry out under reduction or oxidizing condition.When this is reflected at when carrying out under the reducing condition, at least some transition metal are reduced under oxidation state in the original material.When this reaction need not redox and can finish, identical in the product in the oxidation state of metal or hybrid metal and the original material.Can react oxidizing condition is provided by in air, carrying out this.Like this, the oxygen that comes from air is used for the oxidation of the original material that contains this transition metal.
This reaction also utilizes reduction reaction to carry out.For example, this reaction can be carried out in such as hydrogen, ammonia, methane or reducing gas mixture at reducing atmosphere.Alternatively, this reduction reaction comprises in the reactant mixture that by making reducing agent comes in situ (in situ) to carry out, and this reducing agent will be participated in reaction with reducing metal M, but when being used for electrode or electro-chemical cell unit later on, can produce accessory substance, this accessory substance can the interferon activity material.
Alkali metal source comprises any in the multiple salt of lithium, sodium, potassium, rubidium or caesium or the ionic compound.Lithium, sodium and potassium compound are preferred, and lithium is particularly preferred.Preferably, this alkali metal source provides with powder or particulate form.Known in domain of inorganic chemistry have many such materials.Example comprises lithium, the fluoride of sodium and/or potassium, chloride, bromide, iodide, nitrate, nitrite, sulfate, disulfate (hydrogen sulfates), sulphite, bisulfite, carbonate, heavy carbonate, borate, phosphate, ammonium hydrogen phosphate salt (hydrogen ammonium phosphates), biphosphate ammonium salt (dihydrogen ammonium phosphates), silicate, stibate, arsenate, germanate, oxide, acetate, oxalates, and analog.Also can use the hydrate (hydrates) and the mixture of above-claimed cpd.Especially, these mixtures can contain multiple alkali metal, thereby can produce the alkali metal active material that mixes in reaction.
Metal M, M 1, M 2, M 3And M 4The source comprise in transition metal, alkaline-earth metal or lanthanide series and the nontransition metal (such as boron, aluminium, gallium, indium, thallium, germanium, tin, antimony and bismuth) any salt or compound.These slaines or compound comprise fluoride, chloride, bromide, iodide, nitrate, nitrite, sulfate, disulfate, sulphite, bisulfite, carbonate, heavy carbonate, borate, phosphate, ammonium hydrogen phosphate salt, biphosphate ammonium salt, silicate, stibate, arsenate, germanate, oxide, hydroxide, acetate, oxalates and analog thereof.Hydrate also can use.According to the oxidation or the reducing condition of the state of oxidation required in the product of wanting and expection, the metal M in the original material can have any oxidation state, and is as described below.Especially, the cobalt of active material and iron can be by having Co + 2, Co + 3, Fe + 2Or Fe + 3Original material provide.These source metal can be selected like this, and at least a metal can be in than its higher oxidation state in product in the final reacting product.In a preferred embodiment, these source metal also comprise the a+2 nontransition metal.Simultaneously preferably, at least a source metal is the source of a+3 nontransition metal.In comprising the embodiment of Ti, the source of Ti is provided in original material, and, utilizes reduction or non-reduced condition to make these compounds according to the expectation oxidation state of Ti and other metals in other compositions of product and the end product.The suitable presoma that contains Ti comprises TiO 2, Ti 2O 3And TiO.
Except phosphate (or other XY 4Species), outside halide and the hydroxide, also can provide the anionic source of original material of expectation, such as phosphate, halide and hydroxide by containing just charged cationic multiple salt or compound.These cations comprise the ion of following metal, such as alkali metal, alkali metal (potassium, sodium etc.) (alkaline metals), transition metal or other non-transition elements, and complex cation, such as ammonium or quaternary ammonium.Phosphate radical anion in these compounds can be phosphate radical, ammonium hydrogen phosphate root or ammonium dihydrogen phosphate root.Along with above-mentioned alkali metal source and source metal, preferably provide phosphate or other XY with particulate or powder type 4Species, halide and hydroxide original material.The hydrate of any above-claimed cpd can use with above-claimed cpd the samely.
As mentioned above, active material A of the present invention aM b(XY 4) cZ dCan contain XY in the mixture, molecular formula of mixture, the metal M of alkali metal A 4The phosphate radical of group's representative and optional halide or hydroxide Z.In another program of the present invention, phosphate radical can be wholly or in part by a large amount of other XY 4Component replaces, and it is called as " phosphate substituent " or " modified phosphate ".Therefore, active material can provide according to the present invention, in the present invention, and XY 4Component is a phosphate radical, and it can be replaced by following component wholly or in part, such as sulfate radical (SO 4) 2-, a fluorine one phosphate radical (PO 3F) 2-, difluoro list phosphate radical (PO 2F) 2-, silicate (SiO 4) 4-, arsenate, metaantimmonic acid root and germanic acid root.The congener of the above-mentioned oxide anion after some or all of oxygen are replaced by sulphur also is useful in active material of the present invention, but such exception is arranged, and promptly sulfate radical can not fully be replaced by sulphur.For example, sulfo-one phosphate radical also can be used as the substituent wholly or in part of phosphate radical in the active material of the present invention.These sulfo-one phosphoric acid comprise anion radical: (PO 3S) 3-, (PO 2S 2) 3-, (POS 3) 3-(PS 4) 3-But their most convenient ground is as sodium, lithium or potassium derivative.
For the synthetic active material that contains the modified phosphate component, can utilize the replacement negative ion source to substitute above-mentioned all phosphate compoundss or the preferred only part of phosphate compounds usually.This replacement can be considered on the stoichiometry basis.Can provide supply to replace original material and above-mentioned other original materials of negative ion source together.In the non-oxidation reduction, perhaps under oxidation or reducing condition, contain active material synthetic of modified phosphate root (phosphate group) as mentioned above.Identical with the situation of phosphate compounds, the compound that contains modification or replacement phosphate radical can also be the source of other compositions of active material.For example, alkali metal and/or any other metal can be the parts of modified phosphate salt compound.
The limiting examples in one fluorine monophosphate source comprises Na 2PO 3F, K 2PO 3F, NH 4) 2PO 3FH 2O, LiNaPO 3FH 2O, LiKPO 3F, LiNH 4PO 3F, NaNH 4PO 3F, NaK 3(PO 3F) 2And CaPO 3F2H 2O.Two fluorine monophosphate compounds do not comprise NH with limiting 4PO 2F 2, NaPO 2F 2, KPO 2F 2, Al (PO 2F 2) 3And Fe (PO 2F 2) 3
In the time need partially or even wholly replacing phosphate radical in the active material, can utilize multiple silicate and other silicon-containing compounds with silicon.Therefore, the useful source of silicon comprises that orthosilicate, mesosilicate (pyrosilicates), ring-type silicate anion are such as (Si in the active material of the present invention 3O 9) 6-, (Si 6O 18) 12-Deng, and molecular formula [(SiO 3) 2-] nRepresented refractory ceramics (pyrocenes), for example LiAl (SiO 3) 2Silicon or SiO 2Also can use.The phosphatic silicate of local replacement has illustrated in example 4.
Representative arsenate compound in order to preparation active material of the present invention comprises H 3AsO 4And anion radical [H 2AsO 4] -[HAsO 4] 2-Salt.The source of metaantimmonic acid root can be provided by stibium containing material in the active material, such as Sb 2O 5, M ISbO 3(M wherein IBe metal with oxidation state+1), M IIISbO 4(M wherein IIIBe to have+metal of 3 oxidation state) and M IISb 2O 7(M wherein IIBe to have+metal of 2 oxidation state).Other sources of metaantimmonic acid root comprise compound, such as Li 3SbO 4, NH 4H 2SbO 4, and [SbO 4] 3-Otheralkali metal of anion radical and/or ammonium salt-mixture.
The source that can sulphur partially or even wholly replaces the sulphate cpd of the phosphorus in the active material comprises sulfate and the disulfate and the hybrid metal sulfate of alkali metal and transition metal, such as (NH 4) 2Fe (SO 4) 2, NH 4Fe (SO 4) 2Deng.At last, in the time need replacing some or all phosphorus in the active material, can utilize germanium-containing compound, such as GeO with germanium 2
In order to prepare the active material that contains the modified phosphate root, general such carrying out can be satisfied, promptly select the stoichiometry of original material for use, and original material one is reacted according to said process about phosphate material based on the expection stoichiometry of modified phosphate root in the end product.Naturally, partially or even wholly replace phosphate radical, must recomputate the stoichiometry of required original material and calculate with above-mentioned any one modification or replacement phosphate radical.
Original material can provide multiple composition A, M, XY 4And Z, as indicated in the top tabulation.In various embodiment of the present invention, provide for example to comprise metal and phosphatic original material, therefore only need add alkali metal.In one embodiment, provide and for example contain alkali metal, metal and phosphatic original material.As general rule, according to availability, can select original material neatly, it contains alkali metal A, metal M, phosphate (or other XY 4Component) any and among halide or the hydroxide Z, this depends on practicality.Also can use the combination of the original material that each composition is provided.
Generally speaking, any anion can combine with alkali metal cation, so that the alkali metal source original material to be provided, perhaps combines with the metal M cation, so that the metal initial material to be provided.Similarly, any cation can combine with halide or hydroxide anion, and so that the source of Z composition original material to be provided, and any cation can be used as phosphate radical or similar XY 4The counterion of composition (counterion).Yet preferably selection has the original material of counterion, and these counterions cause the formation of volatile byproducts during solid-state reaction.Therefore, need to select possible ammonium salt, carbonate, heavy carbonate, oxide, hydroxide etc.The original material that has these counterions is easy to form volatile byproducts, and such as water, ammonia, carbon dioxide, they can easily be removed from reactant mixture.Similarly, the anion of sulfur-bearing such as sulfate radical, bisulfate ion, inferior sulfate radical, heavy inferior sulfate radical etc., is easy to cause volatility sulfur oxide accessory substance.Nitrogenous anion such as nitrate anion, nitrite anions, also is easy to bring volatile NO xAccessory substance.
As mentioned above, these reactions can be carried out when no reduction or under the effect of reducing agent.In a scheme, for providing the reducing agent of reducing power, these reactions can provide by the form of reduction carbon, and this reduction carbon comprises simple substance carbon and other particulate original materials.At this moment, be oxidized to carbon monoxide simultaneously by carbon or carbon dioxide provides reducing power.
The original material and the carbon that contain transistion metal compound mix, and its contained quantity is enough to reduce the metal ion of one or more containing metal original materials, but incomplete reduction is to elemental metals attitude (excessive reduction carbon can in order to improve product quality).In final electrode mode, play the effect of conductive element in excess carbon residual after the reaction.Because this residual carbon is very closely mixed with its lytic activity material, so this is very favourable.Therefore, can use a large amount of carbon, for example 100% excessive carbon or the more carbon of volume.In a preferred embodiment, the carbon that exists during compound forms can critically be scattered in whole presoma and the product.This provides many advantages, comprises that the conductivity of product strengthens.In a preferred embodiment, carbon particulate is present in the original material also can provide the nucleation site, is used to generate the product crystal.
The source of reduction carbon alternatively or additionally, can be provided by organic material.This organic material is characterised in that and contains carbon and at least a other elements, is preferably hydrogen.Heating in a single day under reaction condition, organic material generally can form catabolite, is meant carbonaceous material here.Be not limited to theory, can impel the representative decomposition technique that forms carbonaceous material to comprise pyrolysis (pyrolization), carbonization, coking, destructive distillation etc.These technology titles and term thermal decomposition are alternately used in this application, can form the technology that can be used as the catabolite of reducing agent when heating the reactant mixture that contains organic material to be illustrated in.
Typical catabolite contains carbonaceous material.Between the stage of reaction in a preferred embodiment, the carbonaceous material that at least a portion forms is participated in reaction as reducing agent.This part of participating in reaction as reducing agent can form volatile byproducts as described below.Any volatile byproducts that forms is easy to break away from from reactant mixture, thereby is not merged among the product.
Although the present invention is understood that to be not limited to the reaction mechanism of organic precursor material, can think that formed carbonaceous material provides the reducing power that is provided to above-mentioned simple substance carbon similar reducing power from organic material decomposes.For example, carbonaceous material produces carbon monoxide or carbon dioxide, and this depends on reaction temperature.
In a preferred embodiment, provide some organic materials of reducing power to be oxidizing to involatile constituent, for example oxygen containing material with carbon element is such as alcohol, ketone, aldehyde, ester, carboxylic acid and acid anhydride.These non-volatile by-products and any carbonaceous material of not participating in reaction as reducing agent are (for example, any material that stoichiometry is excessive or any material that does not react) will be easy to remain in the reactant mixture with other product, but not in a large number covalently (convalently) incorporate into.
Preferably, the carbonaceous material for preparing by heating organic precursor material is rich in carbon with respect to the mole percentage carbon that exists in the organic material.Carbonaceous material preferably contains from about 50 carbon to about 100 molar percentages.
Although in certain embodiments, with respect to simple substance carbon, the organic precursor material has formed the carbon containing catabolite as above-mentioned reducing agent, and in other embodiments, a part of organic material can be used as reducing agent and participates in reaction, and not earlier through decomposing.The invention is not restricted to basic reducing process cutter system really.
As for simple substance carbon, with the reaction of organic precursor material can be by mixing original material and heating is carried out easily.These original materials comprise at least a above-mentioned transistion metal compound.For the purpose of convenient, preferably in a step, carry out the decomposition of organic material and the reduction of transition metal.In this embodiment, this organic material decomposes when transistion metal compound exists, can be to form as the catabolite of reducing agent, and this reducing agent and transistion metal compound reaction are to form the transistion metal compound of reduction.In another embodiment, this organic material can be decomposed in an independent step, to form catabolite.This catabolite makes up with transistion metal compound then, to form mixture.Then, this mixture is heated certain hour under enough temperature, comprises the product of the transistion metal compound of reduction with formation.
This organic precursor material can be any other decomposition technique that can stand any organic material of pyrolysis or destructive distillation or can generate the carbonaceous material that is rich in carbon.These presomas generally comprise any organic material,, are characterised in that the compound that contains carbon and at least a other elements that is.Although this organic material can be the perhalogenation compound (perhalo compound) that contains carbon-free substantially-hydrogen bond, these organic materials contain carbon and hydrogen usually.Other elements such as halogen, oxygen, p and s, can be present in the organic material, as long as they can not disturb decomposable process or prevention to reduce greatly.Presoma comprises organic hydrocarbon, alcohol, ester, ketone, aldehyde, carboxylic acid, sulphonic acid ester (sulfonate) and ether.Preferred presoma comprises the species, particularly aromatic hydrocarbon of above-mentioned aromatic rings, such as tar, pitch and other petroleum products or cut.Here used hydrocarbon (hydrocarbon) is meant the organic compound of being made up of carbon and hydrogen, and contains other elements few in number.Hydrocarbon can comprise and has some heteroatomic impurity.These impurity for example are to be caused such as not exclusively separating the oil from reactant mixture or natural source material by the partial oxidation of hydrocarbon or hydrocarbon.
Other organic precursor materials comprise sugar and other carbohydrate, comprise derivative and polymer.Examples of polymer comprises starch, cellulose and their ether or ester derivant.Other derivatives comprise the carbohydrate of following local reduction and selective oxidation.When heating, carbohydrate decomposes easily to form carbon and water.The terminology used here carbohydrate is contained D-, L-and DL-form and mixture, and comprises the material that comes from nature or man-made resources.
In the present invention, carbohydrate is can be by writing molecular formula (C) m(H 2O) nOrganic material, wherein m and n are integers.For simple hexose or pentose, m and n are equal to each other.Molecular formula C 6H 12O 6The hexose example comprise allose, altrose (altrose), glucose, mannose, gulose (gulose), inositol, galactolipin, talose, sorbose, Tagatose and fructose.Molecular formula C 5H 10O 5Pentose comprise ribose, arabinose and wood sugar.Tetrose comprises erythrose and threose, and glyceraldehyde is triose.Other carbohydrate comprise that general formula is C 12H 22O 11Dicyclo sugar (disaccharides).Example comprises sucrose, maltose, lactose, trehalose, gentiobiose, cellobiose and melibiose.Also can use three ring (trisaccharide is such as melitriose), higher oligomerization and copolymerization carbohydrate.Example comprises starch and cellulose.As mentioned above, when being heated to sufficiently high temperature, carbohydrate is decomposed into carbon and water easily.The water that decomposes is easy to become steam and volatilization under reaction condition.
To understand other materials and also be easy to be decomposed into H 2O and rich material containing carbon.These materials also are intended to be contained in the term used herein " carbohydrate ".These materials comprise the carbohydrate of reduction a little, such as glycerol, sorb (sugar) alcohol, sweet mellow wine, iditol, hexitol, talitol, arabite, xylitol and ribitol, and the carbohydrate of " oxidation a little ", such as gluconic acid, mannopyranose acid, glucuronic acid, galacturonic acid, mannuronic acid, granulated sugar acid, promise granulated sugar acid (manosaccharic) advanced in years, Chinese mugwort Du sand saccharic acid (ido-saccharic), mucic acid, tower dragon mucic acid (talo-mucic aid) and different mucic acid (allo-mucic acid).Oxidation is similar to the molecular formula of carbohydrate with the molecular formula of the carbohydrate that reduces a little a little.
Preferred carbohydrate is a sucrose.Under reaction condition, sucrose is in approximately 150-180 ℃ of thawing.Preferably, liquid state is melted body and is easy to be distributed in the original material.Under about temperature more than 450 ℃, sucrose and other carbohydrate breakdown form carbon and water.The carbon dust that decomposes is the new amorphous fine particles with high surface and high response.
The organic precursor material can also be an organic polymer.Organic polymer comprises polyethylene and polypropylene, butadiene polymer, isoprene copolymer, vinyl alcohol polymer, furfuryl alcohol polymer, styrene polymer (comprising polystyrene, polystyrene-poly butadiene etc.), divinyl benzene polymers, naphthalene polymer, phenol condensation product (comprising those products by reacting and obtain with aldehyde, polyacrylonitrile, polyvinyl acetate and cellulose starch, ester, ether one).
In certain embodiments, the organic precursor material is the solid that can particulate form obtains.According to the method described above, microparticle material can react with other particulate original material combinations and by heating.
In other embodiments, the organic precursor material can be a liquid.At this moment, the combination of liquid precursor material and other particulate original materials is to form mixture.This mixture is heated, so organic material forms carbonaceous material in situ.Carbon thermal reduction is proceeded in this reaction.The liquid precursor material also can be advantageously used for or serve as the adhesive in the above-mentioned original material mixture.
Reduction carbon preferably is used in the reaction with excessive stoichiometry.In order to calculate the relative molecular weight of reduction carbon, utilizing the equivalent weight (equivalent weight) of reduction carbon is easily, and it is defined as every Gram-mole's (gram-mole) of carbon atom weight.For simple substance carbon, such as carbon black, graphite etc., equivalent weight approximately is 12g/ equivalent (g/equivalent).For other organic materials, the equivalent weight of every Gram-mole's carbon atom is bigger.For example, hydrocarbon has the equivalent weight of about 14g/ equivalent.The example of hydrocarbon comprises aliphatic hydrocarbon, alicyclic and aromatic hydrocarbons and the polymer that mainly or all contains carbon and hydrogen in polymer chain.These polymer comprise polyolefin, aromatic polymer, copolymer, comprise polyethylene, polypropylene, polystyrene, polybutadiene etc.According to degree of unsaturation, this equivalent can be slightly more than 14 or below.
For organic material, be used for calculating the equivalent weight of reaction stoichiometric usually greater than 14 with element outside carbon and the hydrogen.For example, it approximately is the 30g/ equivalent in carbohydrate.Examples of carbohydrates comprises sugar, such as glucose, fructose and sucrose, and polymer, such as cellulose, starch.
Although these reactions can be carried out in oxygen or air, preferably in basic non-oxidizing atmosphere, heat.The basic non-oxidation of this atmosphere is in order to avoid disturb the reduction reaction that takes place.The atmosphere of basic non-oxidation can be by utilizing vacuum or obtaining by utilizing inert gas to wait such as argon, nitrogen.Although oxidizing gas (such as oxygen or air) can exist, its concentration should not be so high as to the quality of disturbing carbon thermal reduction or reducing product.Can think that the existence of any oxidizing gas will be easy to and reduce carbon and react and reduce the availability of the carbon of participating in reaction.To a certain extent, such possibility can be expected and excessive reduction carbon is in harmonious proportion as original material by providing suitably.Yet in practice, generally preferably in containing the atmosphere of oxidizing gas seldom, carry out carbon thermal reduction.
In a preferred embodiment, as mentioned above, reduction is carried out in reducing atmosphere when having reducing agent.Terminology used here " reducing atmosphere " meaning is gas or admixture of gas, and it can be provided at the reducing power that is reacted in this atmosphere.Reducing atmosphere preferably contains one or more so-called reducing gass.The example of reducing gas comprises hydrogen, carbon monoxide, methane, ammonia and composition thereof.Reducing atmosphere also preferably has oxidizing gas seldom, such as air or oxygen, or does not have oxidizing gas.If it is oxidizing gas is present in the reducing atmosphere, then preferably few to enough low level, so that can significantly not disturb any reduction process of generation.
The stoichiometry of reduction can be along with initial composition A, M, PO 4(or other XY 4Component) selects with the relative stoichiometric of Z.It is easier usually excessive stoichiometric reducing agent to be provided and to remove excessive thing as required after reaction.Under the situation of reducing gas and utilization reduction carbon ratio such as simple substance carbon or organic material, any excessive reductant can not have problems.In the former case, this gas volatilizees, and be easy to from reactant mixture, separate, and under one situation of back, excess carbon in the product is without detriment to the character of active material, particularly in carbon being added in the active material with the electrode material embodiment that is formed for electro-chemical cell of the present invention unit and battery.Simultaneously easily, accessory substance carbon monoxide or carbon dioxide (under the situation of using carbon) or water (under the situation of using hydrogen) are easy to remove from reactant mixture.
When utilizing reducing atmosphere, be difficult to provide inexcessive reducing gas such as hydrogen.Under these circumstances, preferably, control the stoichiometry of reaction by other reagent of limiting the quantity of.Alternatively, this reaction can be carried out when having reduction carbon ratio such as simple substance carbon.Can utilize the reduction carbon of exact magnitude to prepare selected stoichiometric product experimentally.Yet, preferably, in the carbon of molar excess, carry out carbon thermal reduction.As for reducing atmosphere, be easy to experimentally realize, and make excess carbon be scattered in product easily, as previously mentioned, thereby provide the active electrode material of usefulness.
Make the original material mixture send out should before, the particulate of original material is mixed.Preferably, original material is a particulate form, and mixes the basic precursor powder mixture uniformly of back acquisition.In one embodiment, for example utilizing ball mill to do to these precursor powders mixes.Then, mixed powder compaction is become bead.In another embodiment, precursor powder mixes with adhesive.This adhesive preferably is chosen as the reaction that does not hinder between the powder particle.Preferred adhesive can be lower than decomposition or evaporation under the temperature of reaction temperature.Example comprises mineral oil, glycerine and polymer, these polymer before reaction beginning, decompose or carbonization to form the carbon residue, perhaps evaporation before the reaction beginning.In one embodiment, these adhesives that are used for fixing solia particle are also as the source of reduction carbon, as previously mentioned.In another embodiment, mix, then the particulate that mixes is pressed together with the bead form, contact to provide between good particle by utilizing volatile solvent to form the wet mixing mixture.
The mixture of original material is heated certain hour being enough to form under the temperature of inorganic transistion metal compound product.If original material comprises reducing agent, then reduzate is the transistion metal compound with at least a transition metal, and this transition metal is in lower oxidation state with respect to its oxidation state in original material.
Preferably, the particulate original material is heated to the temperature that is lower than the original material fusing point.Preferably, at least a portion original material during reaction remains on solid-state.
This temperature preferably is about 400 ℃ or higher, and expectation is approximately 450 ℃ or higher, preferably is about 500 ℃ or higher, and generally carries out with faster rate under higher temperature.Various reactions all relate to producing discharges gas CO or CO 2The balance that is reflected under the higher temperature will help forming CO.Some reaction is more wished to carry out in about temperature more than 600 ℃; Most reaction is wished to carry out in about temperature more than 650 ℃; Preferably, about 700 ℃ or more than; More preferably, about 750 ℃ or more than.For many reactions, proper range is from about 700 ℃ to about 950 ℃, perhaps from about 700 ℃ to about 800 ℃.
Generally speaking, the reaction of higher temperature produces CO, and its stoichiometric proportion produces CO at low temperatures 2Need to use more carbon.This is because from C to CO 2The reduction effect of reaction greater than the reduction effect of the reaction from C to CO.From C to CO 2Reaction mean that the oxidation of coal attitude increases+4 (from zero to 4), the reaction from C to CO means that the oxidation of coal attitude increases+2 (from ground state zero to 2).Here, higher temperature typically refers to about 650 ℃ and arrives about 1000 ℃ scope, and lower temperature is meant about at the most 650 ℃.The temperature that is higher than 1200 ℃ is considered to unwanted.
In one embodiment, method of the present invention is utilized the reproducibility of carbon with unique and controlled way, and to produce the product of hope, it has structure and the alkali metal content that is suitable for use as electrode active material.These advantages can be passed through reducing agent (carbon) and realize that at least in part this reducing agent has a kind of oxide, and the formation free energy of this oxide is along with temperature rises and become more negative (negative).The oxide of carbon is at high temperature than more stable at low temperatures.This feature is used to produce the product with one or more metal ions, and these ions are in the oxidation state of reduction with respect to presoma metal ion oxidation state.
Get back in the discussion to temperature, in the time of about 700 ℃, the reaction of carbon to carbon monoxide and carbon to carbon dioxide can take place.More near 600 ℃ the time, C is to CO 2Reaction be key reaction.More near 800 ℃ the time, C is main to the reaction of CO.Because C is to CO 2The reduction effect of reaction stronger, the therefore carbon that the metal needs to be restored of every atomic unit will be still less.Under the situation of carbon monoxide, the carbon of every atomic unit is oxidized to positive divalent from the ground state zeroth order at carbon.Therefore, for the metal ion (M) of the every atomic unit that is reduced an oxidation state, need the carbon of half atomic unit.Under the carbon dioxide reaction situation, concerning the metal ion (M) of every atomic unit of being reduced an oxidation state, on stoichiometry, need the carbon of 1/4th atomic units at carbon because carbon from the ground state zeroth order to positive 4 valency oxidation state.These identical relations are applicable to each this metal ion species that is reduced, and are applicable to the per unit reduction under each expection oxidation state.
Original material can be heated under the slope (ramprate) of 10 ℃ of about per minutes from per minute part degree.Can select higher or lower slope according to available equipment, the turnover of hope (turnaround) and other factors.Original material directly can also be put into preheating furnace.In case reach the reaction temperature of hope, reactant (original material) keeps adequate time under this reaction temperature, so that react.Usually, this is reflected under the end reaction temperature and carries out a few hours.This heating preferably non-oxide or inert gas such as argon or vacuum under or in reducing atmosphere, carry out.
After reaction, preferably, these products are cooled to environment (indoor) temperature (being about 10 ℃ to about 40 ℃) from high temperature.Cooldown rate can change according to various factors (comprising the factor that relates to when the rate of heat addition is discussed).For example, this cooling can be carried out under the speed similar to the initial stage slope.Have been found that such cooldown rate is enough to obtain to have the end product of wishing structure.Can also quench to these products), to realize higher cooldown rate, for example in about 100 ℃/minute grade.
The general approach of above-mentioned synthesis path is applicable to various original materials.Metallic compound can be reduced in the presence of such as hydrogen or carbon at reducing agent.Same consideration is applicable to other metals and the phosphate that contains original material.Consideration on the thermodynamics such as the fusing point of easy reproducibility, kinetics and the salt of selected original material, will be facilitated and regulate whole technical process, such as the quantity of reducing agent, the temperature and the time of staying (dwell time) of reaction.
Electrode:
The present invention also provides the electrode that comprises electrode active material of the present invention.In a preferred embodiment, electrode of the present invention comprises electrode active material of the present invention, adhesive and conduction carbonaceous material.
In a preferred embodiment, electrode of the present invention comprises:
(a) about 25% to about 95%, more preferably, and about 50% to about 90% active material;
(b) about 2% to about 95% electric conducting material (for example carbon black); And
(c) about 3% to about 20% adhesive so that all microparticle materials contact with each other, and does not reduce ionic conductivity.
(except as otherwise noted, all here percentage all refer to percentage by weight).Negative electrode of the present invention preferably includes about 50% to about 90% active material, about 5% to about 30% electric conducting material and the adhesive of aequum.Anode of the present invention preferably includes the adhesive of about 50% electric conducting material to about 95% percentage by weight (for example being preferably graphite) and aequum.
Here useful electric conducting material comprises carbon black, graphite, nickel powder, metal particle, conducting polymer (for example, it is characterized by two key conjugation nets for example polypyrrole and polyacetylene) and composition thereof.Here used adhesive preferably includes polymeric material and extractible plasticizer, is applicable to form the bonding porous compounds.Preferred adhesive comprises that halogenated hydrocarbon polymer is (such as poly-(two chloro-1 of poly-(vinylidene chloride) and, the 4-phenylene) ethene (poly ((dichloro-1,4-phenylene) ethylene)), is fluoridized urethanes (fluorinated urethanes), fluorinated epoxide (fluorinated epoxides), fluorinated acrylic resin, the copolymer of halogenated hydrocarbon polymer, epoxide derivate, ethylene propylene diene rubber (ethylenepropylene diaminetermonomer; EPDM), ethylene propylene diene rubber (ethylene propylenediaminetermonomer; EPDM), polyvinylidene fluoride (PVDF), hexafluoropropylene (HFP), ethylene acrylic acid co polymer (EAA), EVAc (EVA), EAA/EVA copolymer, PVDF/HFP copolymer and composition thereof.
In the selection process of making electrode, electrode active material and polymeric adhesive immunomodulator compounds, solvent, plasticizer and optional electric conducting material are mixed together the pulp thing.This active material slurry is suitably stirred, and utilizes doctor blade to be applied in substrate thinly then.This substrate can be movably (removable) substrate or function substrate, such as the current collector that is attached to electrode film one side (for example, metal grate or mesh layer).In one embodiment, heat or radiation,, stay solid residue from electrode film so that solvent is evaporated.At this moment this electrode film and then be cured heats this film and exerts pressure, so that its sintering and calendering (calendar).In another embodiment, this film can be by air-dry under proper temperature, to generate the self-supported membrane of copolymerization.If this substrate is a movable-type, then it is removed from electrode film, and and then is laminated into current collector.Utilize the substrate of arbitrary type, all must before being incorporated into the battery unit, remove residual plasticizer.
Battery:
Battery of the present invention comprises:
(a) first electrode comprises active material of the present invention;
(b) second electrode, it is the counterelectrode of described first electrode; And
(c) electrolyte between the described electrode.
Electrode active material of the present invention can comprise anode, negative electrode or the two.Preferably, electrode active material comprises negative electrode.
The active material of second electrode (counterelectrode) is the compatible material of electrode active material any and of the present invention.Comprise among the embodiment of negative electrode at electrode active material, anode can comprise any in the various compatible anode material well known in the art, comprise lithium, lithium alloy,, and embed the anode that has such as carbon, tungsten oxide and composition thereof such as the alloy of lithium and aluminium, mercury, manganese, iron, zinc.In a preferred embodiment, anode comprises:
(a) about 0% to about 95%, and preferably approximately 25% to about insert material of 95%, more preferably about 50% to about 90% (insertion material);
(b) about 2% to about 95% electric conducting material (for example carbon black); And
(c) about 3% to about 20% adhesive so that all microparticle materials contact with each other, and does not reduce ionic conductivity.
In particularly preferred embodiment, anode comprises about 50% to about 90% insert material, and this insert material is selected from the active material that metal oxide (transition metal oxide especially), metal chalcogenide and composition thereof constitute.In another preferred embodiment, anode does not contain the embedding active material, but electric conducting material comprises embedding matrix (insertion matrix), and it comprises carbon, graphite, coke, meso carbon (mesocarbon) and composition thereof.It is carbon that one preferred anode inserts material, and such as coke or graphite, it can form compound L i xC.Here useful embedding anode is described in following document to some extent: the distribution on December 23rd, 5,700,298,1997 of people's such as Shi United States Patent (USP); The distribution on 01 27th, 5,712,059,1998 of people's such as Barker United States Patent (USP); The distribution on November 3rd, 5,830,602,1998 of people's such as Barker United States Patent (USP); Saidi etc. be the people's and United States Patent (USP) on 08 15th, 6,103,419,2000 distribution.Here they all are incorporated herein by reference.
Comprise that at electrode active material negative electrode preferably includes among the embodiment of anode:
(a) about 25% to about active material of 95%, more preferably about 50% to about 90%;
(b) about 2% to about 95% electric conducting material (for example carbon black); And
(c) about 3% to about 20% adhesive, so that the closely contact each other of all microparticle materials, and do not reduce ionic conductivity.
Useful active material comprises electrode active material of the present invention in this negative electrode, and metal oxide (transition metal oxide especially), metal chalcogenide and composition thereof.Other active materials comprise the lithia transition metal oxide, such as LiCoO 2, LiNiO 2, and hybrid transition metal oxide, such as LiCo 1-mNi mO 2, 0＜m＜1 wherein.Another preferred active material comprises lithia spinelle active material, and the example is to have LiMn 2O 4The compound of structure, and surface-treated spinelle, 02 month 06 day its calendar year 2001 was disclosed in people's such as Barker United States Patent (USP) 6,183,718, here it was incorporated herein by reference.Also can mix any above-mentioned material that uses two or more.This negative electrode also comprises alkali compounds (basic compound) alternatively to prevent electrode degradation, and description to some extent is incorporated herein by reference it here in the United States Patent (USP) 5,869,207 of distribution on 02 09th, 1999.
Battery of the present invention also comprises suitable electrolyte, and this electrolyte provides the isolation of physical property, but allows ion to move between negative electrode and anode.This electrolyte is preferably such material, and this material list reveals macroion conductivity and has the insulating properties that prevents the memory period self discharge.This electrolyte can be liquid or solid-state.Liquid electrolyte comprises solvent and alkali metal salt, and they form ionic conductivity liquid together.So-called " solid electrolyte " also contains the basis material that is used to isolated electrode.
One preferred embodiment is a solid polymer electrolyte, and it is made up of solid polymer matrix and the salt that is dispersed in this matrix via solvent.Suitable solid polymer matrix comprises well known in the art, and comprise by organic polymer, inorganic polymer or solid matrix forming the solid matrix that monomer forms, and form the solid matrix that the partial polymer of monomer (solid matrix-forming monomer) forms by solid matrix.
In another distortion, polymer, solvent and salt form gel together, and this gel keeps separately electrode, and the ionic conductivity between the electrode is provided.In another distortion, the isolation between the electrode provides by glass fibre mat or other host materials, and this solvent and salt can penetrate the space in this matrix.
Electrolyte of the present invention comprises the salt in the mixture that is dissolved in alkylene carbonate and cyclic ester.Preferably, electrolytical salt is lithium salts or sodium salt.Here these used salt comprise LiAsF 6, LiPF 6, LiClO 4, LiB (C 6H 5) 4, LiAlC1 4, LiBr, LiBF 4, LiSO 3CF 3, LiN (SO 2CF 3) 2, LiN (SO 2C 2F 5) 2And composition thereof and sodium congener (sodium analogs), simultaneously, preferably have a spot of toxicity salt (toxic salts).Salt content is preferably from about 5% to about 65%, preferably from about 8% to about 35% (by electrolytical weight ratio).Preferred salt is LiBF 4In a preferred embodiment, LiBF 4Have the molar concentration from 0.5M to 3M, preferably from 1.0M to 2M, be most preferably about 1.5M.Comprise that the electrolyte compound of used salt is described to some extent here in following document: people's such as Gozdz United States Patent (USP) 5,418,091, the distribution of 05 month 23 days nineteen ninety-five; The distribution in 5,508,130,1996 years 04 month 16 days of the United States Patent (USP) of Golovin; The distribution on 07 30th, 5,541,020,1996 of people's such as Golovin United States Patent (USP); The distribution on 04 15th, 5,620,810,1997 of people's such as Golovin United States Patent (USP); The distribution on 07 01st, 5,643,695,1997 of people's such as Barker United States Patent (USP); The distribution on 01 27th, 5,712,059,1997 of people's such as Barker United States Patent (USP); The distribution on December 22nd, 5,851,504,1998 of people's such as Barker United States Patent (USP); The United States Patent (USP) 6,020,087 of Gao, the distribution of 02 month 01 day calendar year 2001; The distribution on 08 15th, 6,103,419,2000 of people's such as Saidi United States Patent (USP); And people's such as Barker PCT application WO 01/24305,04 month 05 day calendar year 2001 is open, here they all is incorporated herein by reference.
This electrolyte solvent contains the mixture of cyclic ester and alkylene carbonate, alkyl carbonate or its mixture.It is 5 to 8 ring that alkylene carbonate (cyclic carbonate ester (cyclic carbonate)) has preferred size.The carbon atom of this ring is replaced by alkyl alternatively, and this alkyl is preferably rudimentary alkyl (C 1-C 6) chain.Unsubstituted cyclic carbonate ester example is an ethylene carbonate (five-membered ring), 1,3-propylene carbonate (hexatomic ring), 1,4-carbonic acid fourth diester (heptatomic ring) and 1,5-carbonic acid penta diester (octatomic ring).Alternatively, these rings can be replaced by rudimentary alkyl, are preferably methyl, ethyl, propyl group or isopropyl.These structures are known; Example comprises that methyl is for five-membered ring (known 1,2-propylene carbonate or simple propylene carbonate (PC)), and dimethyl for five-membered ring carbonate ester (known 2,3-carbonic acid fourth diester) and ethyl for five-membered ring (known 1,2-carbonic acid fourth diester or simple carbonic acid fourth diester (BC)).Other examples comprise widely methylate, ethylize and third oxidation five to the octatomic ring carbonic ester.In a preferred embodiment, first constituent element is the carbonic ester of five-membered ring or hexatomic ring.More electedly, this cyclic carbonate ester has five-membered ring.In particularly preferred embodiment, alkylene carbonate comprises ethylene carbonate.
Alkyl carbonate is C preferably 1-C 6Alkyl, its at one or more carbon atoms by C 1-C 4Alkyl replaces or is not substituted.Here useful alkyl carbonate comprises diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl ethyl carbonate (EMC) and mixture.Diethyl carbonate is preferred alkyl carbonate.
The carbonic ester composition of electrolyte solvent can comprise alkylene carbonate, alkyl carbonate or its mixture.Preferably, this carbonic ester is an alkylene carbonate.
Electrolyte solvent also comprises cyclic ester, is preferably lactone.Preferred cyclic ester comprises that the size with ring is 4 to 7 cyclic ester.The nuclear carbon atom is replaced by alkyl alternatively, and this alkyl is preferably rudimentary alkyl (C 1-C 6) chain.Unsubstituted cyclic ester example comprises the beta-propiolactone (or simple propiolactone) of four-membered ring; Gamma-butyrolacton (five-membered ring), δ-Wu Neizhi (hexatomic ring) and 6-caprolactone (heptatomic ring).Alternatively, any position of cyclic ester can preferably be replaced by methyl, ethyl, propyl group or isopropyl.Therefore, preferred second embodiment comprise be selected from unsubstitutedly methylate, one or more solvents in ethylization or the propylated lactone, the group that perhaps is selected from propiolactone, butyrolactone, valerolactone and caprolactone formation (will recognize that the alkanisation derivative of some lactones can be named as the different alkanisation derivatives of different core lactone.In order to illustrate, methylated gamma-butyrolacton can be named as gamma-valerolactone on γ-carbon).
In a preferred embodiment, the second constituent element cyclic ester has five to hexatomic ring.Therefore, the preferred second constituent element solvent comprises one or more compounds that are selected from gamma-butyrolacton and the gamma-valerolactone, and methylate, the derivative of ethylization and propyleneization.Preferably, cyclic ester has five-membered ring.In particularly preferred embodiment, the second constituent element cyclic ester comprises gamma-butyrolacton.
Preferred two kinds of constituent element solvent systems contain weight ratio from two kinds of about 1: 20 to 20: 1 constituent elements.More preferably, proportion is from about 1: 10 to about 10: 1, more preferably, and from about 1: 5 to about 5: 1.In the preferred embodiment kind, the quantity of this cyclic ester is more than the quantity of cyclic carbonate ester.Preferably, about at least 60% (weight ratio) of these two kinds of constituent element systems is made up of cyclic ester, and be preferably about 70% or more than.In particularly preferred embodiment, cyclic ester is approximately 3 to 1 with the ratio of cyclic carbonate ester.In one embodiment, this solvent system is made up of gamma-butyrolacton and ethylene carbonate substantially.Therefore, preferred solvent system contains the gamma-butyrolacton of about 3 parts of weight and the ethylene carbonate of about 1 part of weight.Preferred salt and solvent are used together in the preferred mixture, and this mixture is included in the about 1.5 moles LiBF in the solvent of ethylene carbonate of the gamma-butyrolacton that comprises about 3 parts of weight and about 1 part of weight 4
This solvent preferably includes other solvent.These solvents comprise low-molecular-weight organic solvent.Optionally solvent preferably compatible, nonvolatile relatively, dredge protic, polar solvent.The example of useful here optional solvent comprises ether, such as diethylene glycol dimethyl ether, triglyme and tetraethylene glycol dimethyl ether (tetraglyme); Methyl-sulfoxide (dimethylsulfoxide), dioxolanes, sulfolane (sulfolan) and composition thereof.
Barrier film (separator) allows the migration of ion, still provides the physical isolation of electric charge between electrode simultaneously, to prevent short circuit.Polymer substrate self plays the effect of barrier film, and physical isolation required between anode and the negative electrode is provided.Alternatively, electrolyte can contain second or additional polymeric material, with so that play the effect of barrier film.In a preferred embodiment, by reducing temperature to provide infinitely-great resistance to prevent further not controlled reaction, barrier film can prevent the damage that the intensification that occurs at inside battery causes owing to not controlled reaction.
The membrane film element generally is a polymer, and is prepared from by the synthetic that comprises copolymer.Preferred synthetic contains the copolymer and the organic solvent plasticizer of the copolymer of about 75% to about 92% vinylidene fluoride and about 8% to about 25% hexafluoropropylene copolymer (can from the acquisition of Atochem North America as Kynar FLEX commerce).Such copolymer synthetic also is preferably used for preparing the electrode film element, because can guarantee follow-up stacked interface compatibility like this.Plastification solvent can be one of various organic compounds that are commonly used for by the electrolytic salt solvent, for example propylene carbonate or ethylene carbonate, and the mixture of these compounds.More high boiling plasticizer compounds is preferred such as dibutyl phthalate, repefral, diethyl phthalate and tributoxyethyl phosphate (trisbutoxyethylphosphate).Inorganic filling additive, such as forging oxygenerating aluminium (fumed alumina) or silanization fumed silica (silanized fumed silica), can be in order to strengthening the physical strength and the melt viscosity of barrier film, and in some synthetic in order to strengthen the subsequent horizontal that electrolyte dissolution absorbs.In unrestricted embodiment, preferred electrolyte membrance is approximately containing two parts of polymer in each part fumed silica.
Preferred battery comprises the layer-built battery cellular construction, comprises the electrolyte/barrier film between anode layer, cathode layer and anode and the cathode layer.Anode and cathode layer comprise current collector.Preferred current collector is the copper collector foil, is preferably open fine-structure mesh (open mesh grid) form.Current collector is connected in outside flow collection sheet.Such structure example is as open in following document: people's such as Fauteux United States Patent (USP) 4,925,752, the distribution of 05 month 15 days nineteen ninety; The distribution on 04 30th, 5,011,501,1991 of people's such as Shackle United States Patent (USP); And the United States Patent (USP) of Chang distribution in 5,326,653,1994 years 07 month 05 day; Here it all is incorporated herein by reference.In the battery embodiment that comprises a plurality of electro-chemical cells unit, anode strip preferably welds together, and is connected in nickel wire line.Cathode sheets is welded similarly, and is connected to the lead of welding, and each lead has formed the access point of the polarization that is used for external loading thus.
Preferred battery comprises the layer-built battery cellular construction, comprises the electrolyte/barrier film between anode layer, cathode layer and anode and the cathode layer.Anode and negative electrode comprise current collector.Preferred current collector is the copper collector foil, is preferably open fine-structure mesh form.Current collector is connected in outside flow collection sheet, is used to describe sheet and collector.Such structure example is as open in following document: people's such as Fauteux United States Patent (USP) 4,925,752, the distribution of 05 month 15 days nineteen ninety; The distribution on 04 30th, 5,011,501,1991 of people's such as Shackle United States Patent (USP); And the United States Patent (USP) of Chang distribution in 5,326,653,1994 years 07 month 05 day; Here it all is incorporated herein by reference.In the battery embodiment that comprises a plurality of electro-chemical cells unit, anode strip preferably welds together, and is connected in nickel wire line.Cathode sheets is welded similarly, and is connected to the lead of welding, and each lead is formed for the access point of the polarization of external loading thus.
The stacked pressurization between metallic plate under about 120 ℃ of-160 ℃ of temperature by conventional equipment of assembled battery cellular construction realized.After stacked, with after optionally low boiling point solvent extracts plasticizer, the battery unit material can be stored residual plasticizer or be stored as dry plate (drysheet).This plasticizer extracts solvent and non-key, and usually uses methyl alcohol or ether.
In a preferred embodiment, the electrode film that comprises electrode active material (insert material for example, such as carbon or graphite or embed compound) is scattered in the polymer-bonded matrix.Electrolyte/membrane film is the copolymer of plasticising preferably, comprises membrane for polymer and is used for the suitable electrolyte that ion moves.This electrolyte/barrier film is positioned on the electrolyte element, and the positive electrode film that is aggregated in the thing adhesive matrix covers, and this electrode film comprises the composition of the lithiated intercalation compound of fine division.Aluminium current collection film or grid are finished this assembling.The pack material of protectiveness (bagging material) covers this battery unit, and prevents the infiltration of air and moisture.
In another embodiment, the battery structure of many battery units can utilize copper current collector, negative electrode, electrolyte/barrier film, positive electrode and aluminium current collector to prepare.The current collector sheet of elements forms each terminal of this battery structure.
In the preferred embodiment of lithium ion battery, the current collector layer of aluminium foil or grid is covered by positive electrode film or film, and this film is used as and disperses the coating of intercalation electrode synthetic to prepare separately.This preferably embeds compound, and such as the active material of the present invention of the powder type in the polymer matrices solvent, it is dried to form positive electrode.Electrolyte/barrier film is formed the dry coating of synthetic, and it comprises the solution that contains the VdF:HFP copolymer, and plastification solvent is capped on the positive electrode film then.The negative electrode film is formed on the membrane film layer similarly, and this electrode film is formed in the carbon dust that disperses in the copolymer based liquid solution of VdF:HFP or the dry coating of other negative electrode materials.Copper current collector paper tinsel or grid are placed on the positive electrode layer, to finish the battery unit assembling.Therefore, VdF:HFP copolymer synthetic is used as the binder in all main cell components, positive electrode film, negative electrode film and the electrolyte/membrane film.Then, at the parts that add after depressing the heating assembling, with the hot melt adhesive between realization plasticising polymer matrices electrode and the electrolyte synthetic, and hot melt adhesive is to the current collector grid, to form effective lamination of battery unit element thus.This just produces the basic integral body and the battery unit structure of battery flexibly.
The battery unit that comprises useful electrode, electrolyte and other materials is here described in following document to some extent, here it all is incorporated herein by reference: the distribution in 4,668,595,1987 years 05 month 26 days of people's such as Yoshino United States Patent (USP); The distribution on December 20th, 4,792,504,1988 of people's such as Schwab United States Patent (USP); The distribution on 05 26th, 4,830,939,1989 of people's such as Lee United States Patent (USP); The distribution on 06 19th, 4,935,317,1980 of people's such as Fauteaux United States Patent (USP); The distribution on 02 05th, 4,990,413,1991 of people's such as Lee United States Patent (USP); The distribution on 08 06th, 5,037,712,1991 of people's such as Shackle United States Patent (USP); The distribution on November 16th, 5,262,253,1993 of the United States Patent (USP) of Golovin; The distribution in 5,300,373,1994 years 04 month 05 day of the United States Patent (USP) of Shackle; People's such as Chaloner-Gill United States Patent (USP) 5,399,447, the distribution of 03 month 21 days nineteen ninety-five; The United States Patent (USP) 5,411,820 of Chaloner-Gill, the distribution of 05 month 02 day nineteen ninety-five; People's such as Tonder United States Patent (USP) 5,435,054, the distribution of 07 month 25 days nineteen ninety-five; People's such as Chaloner-Gill United States Patent (USP) 5,463,179, distribution on October 31 nineteen ninety-five; The distribution in 5,482,795,1996 years 01 month 09 day of the United States Patent (USP) of Chaloner-Gill; The United States Patent (USP) 5,660,948 of Barker, the distribution of 09 month 16 days nineteen ninety-five; And the United States Patent (USP) 6,306,215 of Larkin, distribution on October 23 calendar year 2001.Preferred electrolyte matrix includes organic polymer, comprises VdF:HFP.Utilize VdF:HFP casting, example stacked and the formation battery unit in following document, to describe to some extent: people's such as Gozdz United States Patent (USP) 5,418,091, the distribution of 05 month 23 days nineteen ninety-five; People's such as Gozdz United States Patent (USP) 5,460,904, distribution on October 24 nineteen ninety-five; People's such as Gozdz United States Patent (USP) 5,456,000, distribution on October 10 nineteen ninety-five; And people's such as Gozdz United States Patent (USP) distribution in 5,540,741,1996 years 07 month 30 days; Here it all is incorporated herein by reference.
The electro-chemical cell unit structure is generally arranged mutually by electrolyte.Liquid state electrolyte battery generally has cylindrical shape, and has a thick over cap, leaks to prevent internal liquid.Liquid state electrolyte battery often since liquid mutually and extension seal cover and seem that with respect to solid electrolyte battery volume is bigger.The miniaturization of solid electrolyte battery energy can form film like.This performance makes to have much bigger flexibility when forming battery and structure storing apparatus.This solid polymer electrolyte battery unit can form dull and stereotyped or prismatic (rectangle) encapsulation, and it can be modified as in design procedure and be fitted in the existing clearance spaces remaining in the electronic device.
Following unrestricted example illustrates synthetic of the present invention and method.
Embodiment 1
Molecular formula is Li 1.025Co 0.9Al 0.025Mg 0.05PO 4As described below manufacturing of electrode active material.The source of Li, Co, Al, Mg and phosphate radical is provided, and it contains mol ratio is 1.025: 0.9: 0.025: 0.05: 1 corresponding constituent element.
0.05125 mole Li 2CO 3(mol.wt.73.88g/mol) 3.8g
0.03 mole Co 3O 4(240.8g/mol) 7.2g
0.0025 mole Al (OH) 3(78g/mol) 0.195g
0.005 mole Mg (OH) 2(58g/mol) 0.29g
0.1 mole (NH 4) 2HPO 4(132g/mol) 13.2g
0.2 mole simple substance carbon (12g/mol) (＞100% is excessive) 2.4g
Mixed and the ball milling of above-mentioned original material is to mix these particulates.Subsequently, particle mixture is granulated.Particulate mixtures is heated 4-20 hour under 750 ℃ in stove in argon gas atmosphere.From stove, this sample is removed and cooled off.X-ray diffractogram shows that this material has the olivine-type crystal structure.Electrode is made with 80% active material, 10% super P (super P) conductive carbon and 10% poly-vinylidene difluoride (poly vinylidene difluoride).Be configured in electrolyte as negative electrode with the battery unit of lithium metal as anode with this electrode, this electrolyte comprises the LiBF of 1M 4, it is dissolved in gamma-butyrolacton: the weight ratio of ethylene carbonate is in 3: 1 the mixture.This active material shows the above invertibity of 140mAhg-1.
Embodiment 2
Molecular formula is Li 1.025Co 0.85Fe 0.05Al 0.025Mg 0.05PO 4(LiCo 0.85Fe 0.05Al 0.025Mg 0.05Li 0.025PO 4) as described below manufacturing of electrode active material.The following source of Li, Co, Fe, Al, Mg and phosphate radical is provided, and it contains mol ratio is 1.025: 0.85: 0.05: 0.025: 0.05: 1 corresponding constituent element.
0.05125 mole Li 2CO 3(mol.wt.73.88g/mol) 3.8g
0.02833 mole Co 3O 4(240.8g/mol) 6.82g
0.0025 mole Fe 2O 3(159.7g/mol) 0.4g
0.0025 mole Al (OH) 3(78g/mol) 0.195g
0.005 mole Mg (OH) 2(58g/mol) 0.29g
0.1 mole (NH 4) 2HPO 4(132g/mol) 13.2g
0.2 mole simple substance carbon (12g/mol) (＞100% is excessive) 2.4g
Mixed and the ball milling of above-mentioned original material is to mix these particulates.Subsequently, particle mixture is granulated.Particulate mixtures is heated 4-20 hour under 750 ℃ in stove in argon gas atmosphere.From stove, this sample is removed and cooled off.X-ray diffractogram shows that this material has the olivine-type crystal structure.Electrode is made with 80% active material, 10% super P (super P) conductive carbon and 10% poly-vinylidene difluoride.Be configured in electrolyte as negative electrode with the battery unit of lithium metal as anode with this electrode, this electrolyte comprises the LiPF of 1M 6, it is dissolved in gamma-butyrolacton: ethylene carbonate: the weight ratio of dimethyl carbonate is in 2: 1: 1 the mixture.
Embodiment 3
Molecular formula Li 1.025Co 0.8Fe 0.1Al 0.025Mg 0.05PO 4(LiCo 0.8Fe 0.1Al 0.025Mg 0.05Li 0.025PO 4) as described below manufacturing of electrode active material.The following source of Li, Co, Fe, Al, Mg and phosphate radical is provided, and it contains mol ratio is 1.025: 0.85: 0.1: 0.025: 0.05: 1 corresponding constituent element.
0.05125 mole Li 2CO 3(mol.wt.73.88g/mol) 3.8g
0.02667 mole Co 3O 4(240.8g/mol) 6.42g
0.005 mole Fe 2O 3(159.7g/mol) 0.8g
0.0025 mole Al (OH) 3(78g/mol) 0.195g
0.005 mole Mg (OH) 2(58g/mol) 0.29g
0.1 mole (NH 4) 2HPO 4(132g/mol) 13.2g
0.2 mole simple substance carbon (12g/mol) (＞100% is excessive) 2.4g
Mixed and the ball milling of above-mentioned original material is to mix these particulates.Subsequently, particle mixture is granulated.Particulate mixtures is heated 4-20 hour under 750 ℃ in stove in argon gas atmosphere.From stove, this sample is removed and cooled off.X-ray diffractogram shows that this material has the olivine-type crystal structure.Electrode is made with 80% active material, 10% super P (super P) conductive carbon and 10% poly-vinylidene difluoride.Be configured in electrolyte with the battery unit of this electrode as negative electrode and carbon embedding anode, this electrolyte comprises the LiPF of 1M 6, it is dissolved in gamma-butyrolacton: the weight ratio of ethylene carbonate is in 3: 1 the mixture.
Embodiment 4
Molecular formula LiCo 0.8Fe 0.05Al 0.1Mg 0.05(PO 4) 0.9(SiO 4) 0.1As described below manufacturing of electrode active material.The following source of Li, Co, Fe, Al, Mg, phosphate radical and silicate is provided, and it contains mol ratio is 1: 0.8: 0.05: 0.1: 0.05: 0.9: 0.1 corresponding constituent element.
0.05 mole Li 2CO 3(mol.wt.73.88g/mol) 3.7g
0.08 mole CoCO 3(118.9g/mol) 9.5g
0.0025 mole Fe 2O 3(159.7g/mol) 0.4g
0.0025 mole Al (OH) 3(78g/mol) 0.195g
0.005 mole Mg (OH) 2(58g/mol) 0.29g
0.09 mole (NH 4) 2HPO 4(132g/mol) 11.9g
0.01 mole SiO 2(60.1g/mol) 0.6g
0.2 mole simple substance carbon (12g/mol) (excessive) 2.4g
Mixed and the ball milling of above-mentioned original material is to mix these particulates.Attention: with respect to 0.05 moles iron in the iron trivalent that will be reduced, this reduction carbon is with excessive existence of approximate 40 times.Subsequently, particle mixture is granulated.Particulate mixtures is heated 4-20 hour under 750 ℃ in stove in argon gas atmosphere.From stove, this sample is removed and cooled off.Electrode is made with 80% active material, 10% super P (super P) conductive carbon and 10% poly-vinylidene difluoride (polyvinylidene difluoride).Be configured in electrolyte with the battery unit of this electrode as negative electrode and carbon embedding anode, this electrolyte comprises the LiBF of 1M 4, it is dissolved in gamma-butyrolacton: the weight ratio of ethylene carbonate is in 3: 1 the mixture.
Embodiment 5
Molecular formula LiCo 0.8Fe 0.1Al 0.025Mg 0.05PO 3.975F 0.025As described below manufacturing of electrode active material.The following source of Li, Co, Fe, Al, Mg, phosphate radical and fluoride is provided, and it contains mol ratio is 1.0: 0.8: 0.1: 0.025: 0.05: 1.0: 0.025 corresponding constituent element.
0.05 mole Li 2CO 3(mol.wt.73.88g/mol), 0.1mol Li 3.7g
0.02667 mole Co 3O 4(240.8g/mol), 0.08mol Co 6.42g
0.005 mole Fe 2O 3(159.7g/mol), 0.01mol Fe 0.8g
0.0025 mole Al (OH) 3(78g/mol), 0.0025mol Al 0.195g
0.005 mole Mg (OH) 2(58g/mol), 0.005mol Mg 0.29g
0.1 mole (NH 4) 2HPO 4(132g/mol), 0.1mol phosphate radical 13.2g
0.00125 mole NH 4HF 2(57g/mol), 0.0025mol F 0.071g
0.2 mole simple substance carbon (12g/mol) (＞100% is excessive) 2.4g
Mixed and the ball milling of above-mentioned original material is to mix these particulates.Subsequently, particle mixture is granulated.Particulate mixtures is heated 4-20 hour under 750 ℃ in stove in argon gas atmosphere.From stove, this sample is removed and cooled off.X-ray diffractogram shows that this material has the olivine-type crystal structure.Electrode is made with 80% active material, 10% super P (super P) conductive carbon and 10% poly-vinylidene difluoride.Be configured in electrolyte with the battery unit of this electrode as negative electrode and carbon embedding anode, this electrolyte comprises the LiBF of 1M 4, it is dissolved in gamma-butyrolacton: the weight ratio of ethylene carbonate is in 3: 1 the mixture.
Embodiment 6
Molecular formula LiFe 0.9Mg 0.1PO 4Electrode active material make according to following reaction equation.
0.50Li 2CO 3+0.45Fe 2O 3+0.10Mg(OH) 2+(NH 4) 2HPO 4+0.45C→LiFe 0.9Mg 0.1PO 4+0.50CO 2+0.45CO+2.0NH 3+1.6H 2O
Utilize mortar and pestle, produce Li by 36.95g (0.50mol) 2CO 3, 71.86g (0.45mol) Fe 2O 3, 5.83g (0.10mol) 0.10Mg (OH) 2, 132.06g (1.0mol) (NH 4) 2HPO 4And the mixture of the carbon of 10.8g (0.90g-mol, 100% is excessive) formation.This mixture is made into granular, and is sent to the temperature control pipe furnace that is equipped with argon stream.This mixture is heated to about 750 ℃ with about 2 ℃/minute slope in inert atmosphere, and keeps about 8 hours under this temperature.Then, this product is cooled to ambient temperature (about 22 ℃).Electrode is made with 80% active material, 10% super P conductive carbon and 10% poly-vinylidene difluoride.Be configured in electrolyte with the battery unit of this electrode as negative electrode and carbon embedding anode, this electrolyte comprises the LiBF of 1M 4, it is dissolved in δ-Wu Neizhi: the weight ratio of ethylene carbonate is in 4: 1 the mixture.
Embodiment 7
Molecular formula Li 1.25Fe 0.9Mg 0.1PO 4F 0.25Electrode active material make according to following reaction equation.
1.0LiFe 0.9Mg 0.1PO 4+d?LiF→Li i+dFe 0.9Mg 0.1PO 4F d
The situation that equals 0.25 for d is with the LiFe of 1.082 grams 0.9Mg 0.1PO 4The LiF premix of (making like that by example 6) and 0.044 gram is also made granularly, is sent in the stove then, and is heated to 700 ℃ final temperature, and kept 15 minutes under this temperature.This sample is cooled off, and from baking oven, remove this sample.For this reaction, almost there is not the loss in weight, lithium fluoride is completely integrated into the phosphate structure, thereby obtains molecular formula Li 1.25Fe 0.9Mg 0.1PO 4F 0.25Active material.Electrode is made with 80% active material, 10% super P conductive carbon and 10% poly-vinylidene difluoride.Be configured in electrolyte with the battery unit of this electrode as negative electrode and carbon embedding anode, this electrolyte comprises the LiBF of 1M 4, it is dissolved in gamma-butyrolacton: the weight ratio of ethylene carbonate is in 3: 1 the mixture.
Embodiment 8
Comprise NaVPO 4The electrode active material of F is made according to following reaction equation.
0.5Na 2CO 3+NH 4F+VPO 4→NaVPO 4F+NH 3+0.5CO 2+0.5H 2O
VPO with 1.23 grams 4, 0.31 the gram NH 4The Na of F and 0.45 gram 2CO 3With approximate 20 milliliters deionized water premixed, and be transferred and be sealed in the Parr Model 4744 acid digestion jars (digestion bomb), this jar is the linear stainless steel reaction vessel of polytetrafluoroethylene (Teflon).This jar is placed in the stove, and is heated to 250 ℃ final temperature, and keeps 48 hours under this temperature.This sample is cooled to room temperature, and takes away to perform an analysis.Utilize deionized water to clean this sample repeatedly, to remove unreacted impurity, under 250 ℃ in argon gas atmosphere dry one hour subsequently.
Embodiment 9
Comprise Li 2.025Co 0.9Al 0.025Mg 0.05PO 4The electrode active material of F is as described below to be made (this case representation contains hybrid metal active material synthetic of lithium and three kinds of different metals, and it is a+2 oxidation state that two kinds of metals are arranged in these three kinds of metals, and a kind of metal is the a+3 oxidation state).For A=Li, a=2.025, M 1=Co, M 2=Al, M 3The situation of=Mg, this reaction is carried out according to following reaction equation.0.5125Li 2CO 3+0.3Co 3(PO 4) 2·8H 2O+0.0125Al 2O 3+0.05Mg(OH) 2+LiF+0.4NH 4H 2PO 4→
Li 2.025Co 0.9Al 0.025Mg 0.05PO 4F+0.5125CO 2+0.4NH 3+8.9H 2O
With the mole shown in top pulverous original material recently is provided, with its mixing, make granularly, and heating four hours in 750 ℃ stove is with the reaction of formation product.Electrode is made with 80% active material, 10% super P conductive carbon and 10% poly-vinylidene difluoride.Be configured in electrolyte with the battery unit of this electrode as negative electrode and carbon embedding anode, this electrolyte comprises the LiBF of 1M 4, it is dissolved in beta-propiolactone: the weight ratio of ethylene carbonate is in 3: 2 the mixture.
Embodiment 10
Contain Li 6V 2(PO 4) 3The electrode active material of F synthesizes according to following equation.
3C+2.5Li 2CO 3+V 2O 5+LiF+3NH 4H 2PO 4→
Li 6V 2(PO 4) 3F+2.5CO 2+3NH 3+4.5H 2O+3CO
This molecular formula indication, carbothermic reduction reaction is accompanied by the generation of carbon monoxide and carries out.Carbon is excessive providing, thus can be with lowest oxidation state+2 of the vanadium of+5 valencys reduction up to it.Think that in this reaction equation this reaction is possible, because enough lithiums are arranged in reaction equation, thereby lithium is integrated in the product, during its quantity is enough to and active material in [(PO 4) 3F] 10-Group.Electrode is made with 80% active material, 10% super P conductive carbon and 10% poly-vinylidene difluoride.Be configured in electrolyte with the battery unit of this electrode as negative electrode and carbon embedding anode, this electrolyte comprises the LiBF of 1M 4, it is dissolved in gamma-butyrolacton: in 3: 1 the mixture of the weight ratio of ethylene carbonate.
Example described here and other embodiment are exemplary, are not the four corner that is intended to restrictively describe synthetic of the present invention and method.Can carry out equivalence to specific embodiment, material, synthetic and method within the scope of the present invention and change, revise and change, all have similar substantially result.

Claims (54)

1. battery comprises:
(a) first electrode comprises molecular formula Li aCo eFe fM 1 gM 2 hM 3 iXY 4Represented olivine structural active material, wherein: (i) 0＜a≤2, e＞0, and f＞0;
(ii) M 1Be one or more transition metal, g 〉=0 wherein;
(iii) M 2Be one or more+2 oxidation state nontransition metal, wherein h 〉=0;
(iv) M 3Be one or more+3 oxidation state nontransition metal, wherein 0.2 〉=i 〉=0.01;
(v) XY 4Be selected from X ' O 4-xY ' x, X ' O 4-yY ' 2y, X " S 4, and composition thereof the group that constitutes, wherein X ' be selected from P, As, Sb, Si, Ge, S, and composition thereof the group that constitutes; X " be selected from the group that P, As, Sb, Si, Ge and composition thereof constitute; Y ' be selected from halogen, S, N, and composition thereof the group that constitutes; 0≤x＜3; And 0＜y≤2;
Wherein 0＜e+f+g+h+i≤2, and M 1, M 2, M 3, XY 4, a, e, f, g, h, i, x and y selected like this, promptly keeps the electric neutrality of this active material;
(b) second electrode, it is the counterelectrode of described first electrode; And
(c) electrolyte.
2. battery as claimed in claim 1, wherein M 3Be be selected from B, Al, Ga, In, and composition thereof the group that constitutes.
3. battery as claimed in claim 1, wherein 0.01≤g≤0.5.
4. battery as claimed in claim 3, wherein M 1Be selected from Ti, V, Cr, Mn, Ni, Cu, and composition thereof the group that constitutes.
5. battery as claimed in claim 1, wherein 0.01≤h≤0.2.
6. battery as claimed in claim 5, wherein M 2Be selected from Be, Mg, Ca, Sr, Ba, and composition thereof the group that constitutes.
7. as each described battery, wherein XY in the claim 1 to 6 4Be PO 4
8. as each described battery, wherein XY in the claim 1 to 6 4Be PO 4-xF x, and 0＜x≤1.
9. as each described battery in the claim 1 to 6, wherein this electrolyte comprises the mixture of cyclic ester and carbonic ester, this carbonic ester be selected from alkyl carbonate, alkylene carbonate, and composition thereof the group that constitutes.
10. battery as claimed in claim 9, wherein this carbonic ester is an alkylene carbonate, it has the ring size of 5 to 8 atoms, and on one or more carbon atoms by C 1-C 6Alkyl replaces or is not substituted.
11. battery as claimed in claim 10, wherein this alkylene carbonate is selected from ethylene carbonate, 1,3-propylene carbonate, 1,4-carbonic acid fourth diester, 1,5-carbonic acid penta diester, 1,2-propylene carbonate, 2,3-carbonic acid fourth diester, 1,2-carbonic acid fourth diester, and composition thereof the group that constitutes.
12. battery as claimed in claim 9, wherein this carbonic ester is carbonic acid C 1-C 6Arrcostab, its on one or more carbon atoms by C 1-C 4Alkyl replaces or is not substituted.
13. battery as claimed in claim 12, wherein this alkyl carbonate be selected from diethyl carbonate, methyl ethyl carbonate, dimethyl carbonate, and composition thereof the group that constitutes.
14. battery as claimed in claim 9, wherein this cyclic ester has the ring size of 4 to 7 atoms, and is replaced by low alkyl group on one or more carbon atoms or be not substituted.
15. battery as claimed in claim 14, wherein this cyclic ester be selected from substituted or unsubstituted beta-propiolactone, substituted or unsubstituted gamma-butyrolacton, substituted or unsubstituted δ-Wu Neizhi, substituted or unsubstituted 6-caprolactone, and composition thereof the group that constitutes.
16. as each described battery in the claim 1 to 6, wherein this second electrode comprises insert material, this insert material is selected from the group that metal chalcogenide, carbon and composition thereof constitute.
17. battery as claimed in claim 16, wherein said metal chalcogenide are metal oxide.
18. battery as claimed in claim 16, wherein said carbon are graphite.
19. a battery comprises:
(a) first electrode comprises molecular formula Li aCo eFe fM 1 gM 2 hM 3 iXY 4Represented olivine structural active material, wherein:
(i) 0＜a≤2, e＞0, and f＞0;
(ii) M 1Be one or more transition metal, g 〉=0 wherein;
(iii) M 2Be one or more+2 oxidation state nontransition metal, wherein 0.2 〉=h 〉=0.01;
(iv) M 3Be one or more+3 oxidation state nontransition metal, wherein i 〉=0;
(v) XY 4Be selected from X ' O 4-xY ' x, X ' O 4-yY ' 2y, X " S 4, and composition thereof the group that constitutes, wherein X ' be selected from P, As, Sb, Si, Ge, S, and composition thereof the group that constitutes; X " be selected from the group that P, As, Sb, Si, Ge and composition thereof constitute; Y ' be selected from halogen, S, N, and composition thereof the group that constitutes; 0≤x＜3; And 0＜y≤2;
Wherein 0＜e+f+g+h+i≤2, and M 1, M 2, M 3, XY 4, a, e, f, g, h, i, x and y selected like this, promptly keeps the electric neutrality of this active material;
(b) second electrode, it is the counterelectrode of described first electrode; And
(c) electrolyte.
20. battery as claimed in claim 19, wherein M 2Be selected from Be, Mg, Ca, Sr, Ba, and composition thereof the group that constitutes.
21. battery as claimed in claim 19, wherein 0.01≤g≤0.5.
22. battery as claimed in claim 21, wherein M 1Be selected from Ti, V, Cr, Mn, Ni, Cu, and composition thereof the group that constitutes.
23. battery as claimed in claim 19, wherein 0.01≤i≤0.2.
24. battery as claimed in claim 23, wherein M 3Be be selected from B, Al, Ga, In, and composition thereof the group that constitutes.
25. as each described battery, wherein XY in the claim 19 to 24 4Be PO 4
26. as each described battery, wherein XY in the claim 19 to 24 4Be PO 4-xF x, and 0＜x≤1.
27. as each described battery in the claim 19 to 24, wherein this electrolyte comprises the mixture of cyclic ester and carbonic ester, this carbonic ester be selected from alkyl carbonate, alkylene carbonate, and composition thereof the group that constitutes.
28. battery as claimed in claim 27, wherein this carbonic ester is an alkylene carbonate, and it has the ring size of 5 to 8 atoms, and on one or more carbon atoms by C 1-C 6Alkyl replaces or is not substituted.
29. battery as claimed in claim 28, wherein this alkylene carbonate is selected from ethylene carbonate, 1,3-propylene carbonate, 1,4-carbonic acid fourth diester, 1,5-carbonic acid penta diester, 1,2-propylene carbonate, 2,3-carbonic acid fourth diester, 1,2-carbonic acid fourth diester, and composition thereof the group that constitutes.
30. battery as claimed in claim 27, wherein this carbonic ester is carbonic acid C 1-C 6Arrcostab, its on one or more carbon atoms by C 1-C 4Alkyl replaces or is not substituted.
31. battery as claimed in claim 30, wherein this alkyl carbonate be selected from diethyl carbonate, methyl ethyl carbonate, dimethyl carbonate, and composition thereof the group that constitutes.
32. battery as claimed in claim 27, wherein this cyclic ester has the ring size of 4 to 7 atoms, and is replaced by low alkyl group on one or more carbon atoms or be not substituted.
33. battery as claimed in claim 32, wherein this cyclic ester be selected from substituted or unsubstituted beta-propiolactone, substituted or unsubstituted gamma-butyrolacton, substituted or unsubstituted δ-Wu Neizhi, substituted or unsubstituted 6-caprolactone, and composition thereof the group that constitutes.
34. as each described battery in the claim 19 to 24, wherein this second electrode comprises insert material, this insert material is selected from the group that metal chalcogenide, carbon and composition thereof constitute.
35. battery as claimed in claim 34, wherein said metal chalcogenide are metal oxide.
36. battery as claimed in claim 34, wherein said carbon are graphite.
37. a battery comprises:
(a) first electrode comprises molecular formula Li aCo eFe fM 1 gM 2 hM 3 iXY 4Represented olivine structural active material, wherein:
(i) 0＜a≤2, e＞0, and f＞0;
(ii) M 1Be one or more transition metal, 0.5 〉=g 〉=0.01 wherein;
(iii) M 2Be one or more+2 oxidation state nontransition metal, wherein h 〉=0;
(iv) M 3Be one or more+3 oxidation state nontransition metal, wherein i 〉=0;
(v) XY 4Be selected from X ' O 4-xY ' x, X ' O 4-yY ' 2y, X " S 4, and composition thereof the group that constitutes, wherein X ' be selected from P, As, Sb, Si, Ge, S, and composition thereof the group that constitutes; X " be selected from the group that P, As, Sb, Si, Ge and composition thereof constitute; Y ' be selected from halogen, S, N, and composition thereof the group that constitutes; 0≤x＜3; And 0＜y≤2;
Wherein 0＜e+f+g+h+i≤2, and M 1, M 2, M 3, XY 4, a, e, f, g, h, i, x and y selected like this, promptly keeps the electric neutrality of this active material;
(b) second electrode, it is the counterelectrode of described first electrode; And
(c) electrolyte.
38. battery as claimed in claim 37, wherein M 1Be selected from Ti, V, Cr, Mn, Ni, Cu, and composition thereof the group that constitutes.
39. battery as claimed in claim 37, wherein 0.01≤h≤0.2.
40. battery as claimed in claim 39, wherein M 2Be selected from Be, Mg, Ca, Sr, Ba, and composition thereof the group that constitutes.
41. battery as claimed in claim 37, wherein 0.01≤i≤0.2.
42. battery as claimed in claim 41, wherein M 3Be be selected from B, Al, Ga, In, and composition thereof the group that constitutes.
43. as each described battery, wherein XY in the claim 37 to 42 4Be PO 4
44. as each described battery, wherein XY in the claim 37 to 42 4Be PO 4-xF x, and 0＜x≤1.
45. as each described battery in the claim 37 to 42, wherein this electrolyte comprises the mixture of cyclic ester and carbonic ester, this carbonic ester be selected from alkyl carbonate, alkylene carbonate, and composition thereof the group that constitutes.
46. battery as claimed in claim 45, wherein this carbonic ester is an alkylene carbonate, and it has the ring size of 5 to 8 atoms, and on one or more carbon atoms by C 1-C 6Alkyl replaces or is not substituted.
47. battery as claimed in claim 46, wherein this alkylene carbonate is selected from ethylene carbonate, 1,3-propylene carbonate, 1,4-carbonic acid fourth diester, 1,5-carbonic acid penta diester, 1,2-propylene carbonate, 2,3-carbonic acid fourth diester, 1,2-carbonic acid fourth diester, and composition thereof the group that constitutes.
48. battery as claimed in claim 45, wherein this carbonic ester is carbonic acid C 1-C 6Arrcostab, its on one or more carbon atoms by C 1-C 4Alkyl replaces or is not substituted.
49. battery as claimed in claim 45, wherein this alkyl carbonate be selected from diethyl carbonate, methyl ethyl carbonate, dimethyl carbonate, and composition thereof the group that constitutes.
50. battery as claimed in claim 45, wherein this cyclic ester has the ring size of 4 to 7 atoms, and is replaced by low alkyl group on one or more carbon atoms or be not substituted.
51. battery as claimed in claim 50, wherein this cyclic ester be selected from substituted or unsubstituted beta-propiolactone, substituted or unsubstituted gamma-butyrolacton, substituted or unsubstituted δ-Wu Neizhi, substituted or unsubstituted 6-caprolactone, and composition thereof the group that constitutes.
52. as each described battery in the claim 37 to 42, wherein this second electrode comprises insert material, this insert material is selected from the group that metal chalcogenide, carbon and composition thereof constitute.
53. battery as claimed in claim 52, wherein said metal chalcogenide are metal oxide.
54. battery as claimed in claim 52, wherein said carbon are graphite.
CN038100339A 2002-04-03 2003-03-27 Batteries comprising alkali-transition metal phosphates and preferred electrolytes Expired - Fee Related CN1650450B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10/116,276 US20030190527A1 (en) 2002-04-03 2002-04-03 Batteries comprising alkali-transition metal phosphates and preferred electrolytes
US10/116,276 2002-04-03
PCT/US2003/009634 WO2003085757A1 (en) 2002-04-03 2003-03-27 Batteries comprising alkali-transition metal phosphates and preferred electrolytes

Publications (2)

Publication Number Publication Date
CN1650450A CN1650450A (en) 2005-08-03
CN1650450B true CN1650450B (en) 2010-04-28

Family

ID=28673938

Family Applications (1)

Application Number Title Priority Date Filing Date
CN038100339A Expired - Fee Related CN1650450B (en) 2002-04-03 2003-03-27 Batteries comprising alkali-transition metal phosphates and preferred electrolytes

Country Status (8)

Country Link
US (2) US20030190527A1 (en)
EP (1) EP1490917A4 (en)
JP (1) JP4758610B2 (en)
KR (1) KR101107423B1 (en)
CN (1) CN1650450B (en)
AU (1) AU2003224801A1 (en)
CA (1) CA2479790C (en)
WO (1) WO2003085757A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10326164B2 (en) 2015-03-03 2019-06-18 Ut-Battelle, Llc High-conduction GE substituted LiAsS4 solid electrolyte

Families Citing this family (83)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8367036B2 (en) * 2000-04-27 2013-02-05 Valence Technology, Inc. Alkali/transition metal halo-and hydroxy-phosphates and related electrode active materials
US8057769B2 (en) * 2000-04-27 2011-11-15 Valence Technology, Inc. Method for making phosphate-based electrode active materials
US6777132B2 (en) * 2000-04-27 2004-08-17 Valence Technology, Inc. Alkali/transition metal halo—and hydroxy-phosphates and related electrode active materials
US7524584B2 (en) 2000-04-27 2009-04-28 Valence Technology, Inc. Electrode active material for a secondary electrochemical cell
US6964827B2 (en) * 2000-04-27 2005-11-15 Valence Technology, Inc. Alkali/transition metal halo- and hydroxy-phosphates and related electrode active materials
CA2455540C (en) * 2002-12-19 2012-08-28 Valence Technology, Inc. Electrode active material and method of making the same
JP4192635B2 (en) * 2003-03-04 2008-12-10 ソニー株式会社 Lithium ion secondary battery electrolyte and lithium ion secondary battery using the same
US7041239B2 (en) * 2003-04-03 2006-05-09 Valence Technology, Inc. Electrodes comprising mixed active particles
US20070141468A1 (en) * 2003-04-03 2007-06-21 Jeremy Barker Electrodes Comprising Mixed Active Particles
CA2539723A1 (en) 2003-09-22 2005-04-07 Valence Technology, Inc. Electrical systems, power supply apparatuses, and power supply operations methods
WO2005041327A1 (en) 2003-10-27 2005-05-06 Mitsui Engineering & Shipbuilding Co.,Ltd. Positive electrode material for secondary battery, method for producing positive electrode material for secondary battery, and secondary battery
FR2864348B1 (en) * 2003-12-18 2006-03-10 Commissariat Energie Atomique LITHIUM ACCUMULATOR HAVING BOTH ELECTRICAL POTENTIAL AND HIGH LTHIUM INSERTION CAPABILITY.
US7008726B2 (en) * 2004-01-22 2006-03-07 Valence Technology, Inc. Secondary battery electrode active materials and methods for making the same
US20050163699A1 (en) * 2004-01-23 2005-07-28 Jeremy Barker Fluorosulfate-based electrode active materials and method of making the same
US7719227B2 (en) 2004-02-13 2010-05-18 Valence Technology, Inc. Electrical energy supply methods and electrical energy power supplies
JP5043290B2 (en) * 2004-06-08 2012-10-10 パナソニック株式会社 Cathode active material for nonaqueous electrolyte secondary battery, method for producing the same, and nonaqueous electrolyte secondary battery using the same
JP4703985B2 (en) * 2004-08-02 2011-06-15 住友大阪セメント株式会社 Method for producing positive electrode active material for lithium battery
WO2006086156A2 (en) * 2005-02-08 2006-08-17 Valence Technology, Inc. Method and apparatus for dissipation of heat generated by a secondary electrochemical cell
US7700236B2 (en) * 2005-09-09 2010-04-20 Aquire Energy Co., Ltd. Cathode material for manufacturing a rechargeable battery
US8323832B2 (en) 2005-08-08 2012-12-04 A123 Systems, Inc. Nanoscale ion storage materials
US8158090B2 (en) 2005-08-08 2012-04-17 A123 Systems, Inc. Amorphous and partially amorphous nanoscale ion storage materials
US7939201B2 (en) 2005-08-08 2011-05-10 A123 Systems, Inc. Nanoscale ion storage materials including co-existing phases or solid solutions
KR100901535B1 (en) * 2005-10-26 2009-06-08 주식회사 엘지화학 Secondary Battery of Improved Life Characteristics
US7906238B2 (en) * 2005-12-23 2011-03-15 3M Innovative Properties Company Silicon-containing alloys useful as electrodes for lithium-ion batteries
US7723958B2 (en) 2006-03-31 2010-05-25 Valence Technology, Inc. Battery charge indication methods, battery charge monitoring devices, rechargeable batteries, and articles of manufacture
US20070298317A1 (en) * 2006-05-09 2007-12-27 Ralph Brodd Secondary electrochemical cell with increased current collecting efficiency
WO2008013317A1 (en) * 2006-07-28 2008-01-31 Sumitomo Chemical Company, Limited Metal phosphate
JP5127179B2 (en) * 2006-07-31 2013-01-23 古河電池株式会社 Method for producing positive electrode active material for lithium secondary battery
WO2008048995A2 (en) 2006-10-17 2008-04-24 Valence Technology, Inc. Method and apparatus for monitoring and controlling an electrochemical cell
US20080261113A1 (en) * 2006-11-15 2008-10-23 Haitao Huang Secondary electrochemical cell with high rate capability
US8288997B2 (en) * 2007-08-24 2012-10-16 Alexander Choi Providing power based on state of charge
TWI466370B (en) 2008-01-17 2014-12-21 A123 Systems Inc Mixed metal olivine electrode materials for lithium ion batteries
CN101489351B (en) * 2008-01-18 2012-10-31 郑州泰达电子材料科技有限公司 Built-in solid electrolytic capacitor for circuit board and circuit board using the built-in solid electrolytic capacitor of circuit board
JP5370937B2 (en) * 2008-01-28 2013-12-18 シャープ株式会社 Positive electrode active material, positive electrode and non-aqueous secondary battery
JP5431452B2 (en) * 2008-04-07 2014-03-05 カーネギー メロン ユニバーシティ Aqueous electrolyte-based electrochemical secondary energy storage device using sodium ions
CN101339992B (en) * 2008-08-04 2010-06-16 清华大学 Preparation of lithium ionic cell positive electrode material vanadium lithium silicate
JP5107213B2 (en) * 2008-11-18 2012-12-26 シャープ株式会社 Positive electrode active material, positive electrode and non-aqueous secondary battery
EP2209153B1 (en) * 2008-12-30 2012-01-25 Hengdian Group DMEGC Magnetic Limited Company Lithium iron phosphate battery electrode and method for manufacturing the same
KR101336562B1 (en) 2009-05-22 2013-12-03 고쿠리츠 다이가쿠 호진 교토 다이가쿠 Cathode active material, cathode and nonaqueous secondary cell
KR101865419B1 (en) 2009-08-25 2018-06-07 에이일이삼 시스템즈, 엘엘씨 Mixed metal olivine electrode materials for lithium ion batteries having improved specific capacity and energy density
JP2011071114A (en) * 2009-08-28 2011-04-07 Equos Research Co Ltd Positive active material for lithium ion battery and lithium ion battery using the same
JP5551019B2 (en) * 2009-09-02 2014-07-16 シャープ株式会社 Positive electrode active material, positive electrode and non-aqueous secondary battery
US9174846B2 (en) 2009-09-18 2015-11-03 A123 Systems Llc Ferric phosphate and methods of preparation thereof
US9660267B2 (en) 2009-09-18 2017-05-23 A123 Systems, LLC High power electrode materials
CN102246333A (en) * 2009-09-18 2011-11-16 松下电器产业株式会社 Electrode for non-aqueous electrolyte secondary cell, method for producing same, and non-aqueous electrolyte secondary cell
KR20120088675A (en) * 2009-09-24 2012-08-08 발렌스 테크놀로지, 인코포레이티드 Manganese phosphates and related electrode active materials
WO2011038499A1 (en) * 2009-10-02 2011-04-07 Linda Faye Nazar Sodium metal phosphate olivines for sodium-ion batteries
KR20110110729A (en) * 2010-04-01 2011-10-07 주식회사 엘지화학 Novel positive electrode for secondary battery
JP5271975B2 (en) 2010-07-01 2013-08-21 シャープ株式会社 Positive electrode active material, positive electrode and non-aqueous electrolyte secondary battery
US9373844B2 (en) 2010-07-01 2016-06-21 Sharp Kabushiki Kaisha Positive electrode active substance containing lithium-containing metal oxide
JP5843766B2 (en) 2010-07-01 2016-01-13 シャープ株式会社 Positive electrode active material, positive electrode and non-aqueous secondary battery
JP5132727B2 (en) 2010-07-12 2013-01-30 シャープ株式会社 Positive electrode active material, positive electrode and non-aqueous electrolyte secondary battery
KR101219395B1 (en) * 2010-07-15 2013-01-11 전자부품연구원 Anode Material for Lithium Secondary Battery and Manufacturing Method of the Same
US20120138867A1 (en) * 2010-11-11 2012-06-07 Phostech Lithium Inc. Carbon-deposited alkali metal oxyanion electrode material and process for preparing same
CN103384931B (en) 2010-12-23 2016-03-30 野猫技术开发公司 There is the lithium ion accumulator material of improved performance
WO2012148569A2 (en) 2011-03-01 2012-11-01 Aquion Energy Inc. Profile responsive electrode ensemble
US8298701B2 (en) 2011-03-09 2012-10-30 Aquion Energy Inc. Aqueous electrolyte energy storage device
JP5451671B2 (en) 2011-03-23 2014-03-26 シャープ株式会社 Positive electrode active material, positive electrode and non-aqueous secondary battery
JP5451681B2 (en) 2011-05-09 2014-03-26 シャープ株式会社 Positive electrode active material, positive electrode and non-aqueous secondary battery
JP5731278B2 (en) * 2011-05-24 2015-06-10 株式会社オハラ All-solid-state lithium ion battery
US8945751B2 (en) 2011-07-19 2015-02-03 Aquion Energy, Inc. High voltage battery composed of anode limited electrochemical cells
US8137830B2 (en) 2011-07-19 2012-03-20 Aquion Energy, Inc. High voltage battery composed of anode limited electrochemical cells
KR101316066B1 (en) * 2011-09-27 2013-10-11 전자부품연구원 Cathode Material for Secondary Battery and Manufacturing Method of the Same
JP5818086B2 (en) * 2011-10-14 2015-11-18 トヨタ自動車株式会社 Secondary battery and manufacturing method thereof
WO2013108570A1 (en) * 2012-01-17 2013-07-25 シャープ株式会社 Positive electrode active material, positive electrode and non-aqueous rechargeable battery
CN102569889A (en) * 2012-02-06 2012-07-11 深圳新宙邦科技股份有限公司 Non-aqueous electrolyte for lithium ion battery, and lithium ion battery
US8652672B2 (en) 2012-03-15 2014-02-18 Aquion Energy, Inc. Large format electrochemical energy storage device housing and module
CN102664267B (en) * 2012-04-13 2015-04-22 浙江工业大学 Co-doped cathode material lithium-vanadium-phosphate and application thereof
KR101946012B1 (en) * 2012-07-11 2019-02-08 삼성전자주식회사 Lithium ion conductor, electrolyte including the same, active material including the same and battery including lithium ion conductor
US8945756B2 (en) 2012-12-12 2015-02-03 Aquion Energy Inc. Composite anode structure for aqueous electrolyte energy storage and device containing same
US9356291B2 (en) 2013-12-04 2016-05-31 The United States Of America, As Represented By The Secretary Of The Army High voltage lithium ion positive electrode material
WO2015153485A1 (en) 2014-04-01 2015-10-08 The Research Foundation For The State University Of New York Electrode materials for group ii cation-based batteries
EP2947713B1 (en) * 2014-05-20 2017-10-04 The United States of America as represented by the Secretary of the Army High voltage lithium ion positive electrode material
CN105742698B (en) * 2014-12-12 2018-02-13 中国科学院物理研究所 NASICON type sodion solid electrolytes materials and preparation method thereof
CN106058250A (en) * 2016-07-22 2016-10-26 天津巴莫科技股份有限公司 Lithium-enriched lithium vanadium phosphate fluoride anode material
US10826145B2 (en) 2017-02-10 2020-11-03 General Electric Company Electrochemical cell for use in high temperature metal-air battery
CN108390026B (en) * 2018-01-22 2020-07-14 李慧 Cage type positive electrode material and preparation method and application thereof
US11251430B2 (en) 2018-03-05 2022-02-15 The Research Foundation For The State University Of New York ϵ-VOPO4 cathode for lithium ion batteries
US20210005925A1 (en) * 2018-03-26 2021-01-07 Toyota Motor Europe Solid electrolyte material for solid state batteries, solid electrolyte and solid state battery
JP7221949B2 (en) * 2020-02-19 2023-02-14 寧徳新能源科技有限公司 Positive plates, electrochemical devices and electronic devices containing positive plates
US11515566B2 (en) 2020-04-26 2022-11-29 International Business Machines Corporation Liquid cathode formulation for rechargeable metal halide battery
EP4143911A1 (en) * 2020-04-26 2023-03-08 International Business Machines Corporation Liquid cathode formulation for rechargeable metal halide battery
WO2023206397A1 (en) * 2022-04-29 2023-11-02 宁德时代新能源科技股份有限公司 Secondary battery, battery module, battery pack and electrical device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6085015A (en) * 1997-03-25 2000-07-04 Hydro-Quebec Lithium insertion electrode materials based on orthosilicate derivatives
US6153333A (en) * 1999-03-23 2000-11-28 Valence Technology, Inc. Lithium-containing phosphate active materials

Family Cites Families (104)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049891A (en) * 1976-06-21 1977-09-20 Massachusetts Institute Of Technology Compositions for fast alkali-metal-ion transport
US4194062A (en) * 1978-07-27 1980-03-18 Bell Telephone Laboratories, Incorporated Rechargeable dichalcogenide cell
IT1131478B (en) * 1980-05-13 1986-06-25 Consiglio Nazionale Ricerche HIGH SPECIFIC ENERGY RECHARGEABLE BATTERIES WITH INTERCALATION ANODE AND CATHODE
US4477541A (en) * 1982-12-22 1984-10-16 The United States Of America As Represented By The United States Department Of Energy Solid electrolyte structure
DE3680249D1 (en) * 1985-05-10 1991-08-22 Asahi Chemical Ind SECONDARY BATTERY.
US4840858A (en) * 1987-06-12 1989-06-20 Sanyo Electric Co., Ltd. Secondary cell
US4792504A (en) * 1987-09-18 1988-12-20 Mhb Joint Venture Liquid containing polymer networks as solid electrolytes
US5037712A (en) * 1987-10-30 1991-08-06 Ultracell, Inc. Preparation of radiation cured solid electrolytes and electrochemical devices employing the same
US4830939B1 (en) * 1987-10-30 1996-10-08 Mhb Joint Venture Radiation cured solid electrolytes and electrochemical devices employing the same
US4990413A (en) * 1989-01-18 1991-02-05 Mhb Joint Venture Composite solid electrolytes and electrochemical devices employing the same
US4925752A (en) * 1989-03-03 1990-05-15 Fauteux Denis G Solid state electrochemical cell having porous cathode current collector
US5011501A (en) * 1989-04-26 1991-04-30 Shackle Dale R Process for making a solid state cell
US5028500A (en) * 1989-05-11 1991-07-02 Moli Energy Limited Carbonaceous electrodes for lithium cells
US4935317A (en) * 1989-06-21 1990-06-19 Mhb Joint Venture Method for producing solid state electrochemical laminar cell utilizing cathode rolling step
CA2052317C (en) * 1990-09-28 1995-09-26 Norio Takami Nonaqueous electrolyte secondary battery
US5130211A (en) * 1990-10-24 1992-07-14 Her Majesty The Queen In Right Of The Provence Of British Columbia Electrolyte solution sequestering agents for electrochemical cells having carbonaceous electrodes
US5686138A (en) * 1991-11-12 1997-11-11 Sanyo Electric Co., Ltd. Lithium secondary battery
US5252413A (en) * 1992-04-07 1993-10-12 Eic Laboratories, Inc. Solid polymer electrolyte lithium batteries
CA2096386A1 (en) * 1992-05-18 1993-11-19 Masahiro Kamauchi Lithium secondary battery
EP0573266B1 (en) * 1992-06-01 1999-12-08 Kabushiki Kaisha Toshiba Lithium secondary battery and method of manufacturing carbonaceous material for negative electrode of the battery
US5508130A (en) * 1992-07-22 1996-04-16 Golovin; Milton N. Solid electrolytes containing LiN(SO2 CF3)2 and a triglyme-carbonate solvent, and electrochemical cells produced therefrom
US5620810A (en) * 1992-07-22 1997-04-15 Valence Technology, Inc. Solid, solvent-containing electrolytes and electrolytic cells produced therefrom
US5262253A (en) * 1992-07-22 1993-11-16 Valence Technology, Inc. Solid electrolytes derived by polymerization of vinyl sulfonate polyalkylene oxides
US5538811A (en) * 1992-07-23 1996-07-23 Matsushita Electric Industrial Co., Ltd. Ionic conductive polymer electrolyte
US5300373A (en) * 1992-09-11 1994-04-05 Valence Technology, Inc. Electrochemical cell stack and method of making an electrochemical cell stack
US5326653A (en) * 1992-10-29 1994-07-05 Valence Technology, Inc. Battery unit with reinforced current collector tabs and method of making a battery unit having strengthened current collector tabs
US5418090A (en) * 1993-02-17 1995-05-23 Valence Technology, Inc. Electrodes for rechargeable lithium batteries
US5460904A (en) * 1993-08-23 1995-10-24 Bell Communications Research, Inc. Electrolyte activatable lithium-ion rechargeable battery cell
US5540741A (en) * 1993-03-05 1996-07-30 Bell Communications Research, Inc. Lithium secondary battery extraction method
US5418091A (en) * 1993-03-05 1995-05-23 Bell Communications Research, Inc. Polymeric electrolytic cell separator membrane
US5240790A (en) * 1993-03-10 1993-08-31 Alliant Techsystems Inc. Lithium-based polymer electrolyte electrochemical cell
US5411820A (en) * 1993-06-08 1995-05-02 Valence Technology, Inc. Solid, glyme-containing electrolytes including ion salt derivatives and electrolytic cells produced therefrom
US5541020A (en) * 1993-07-22 1996-07-30 Golovin; Milton N. Compositions and methods for improving the cumulative capacity of solid, secondary electrolytic cells
US5435054A (en) * 1993-11-15 1995-07-25 Valence Technology, Inc. Method for producing electrochemical cell
US5399447A (en) * 1993-12-06 1995-03-21 Valence Technology, Inc. Acidity reduction of adhesion promoter layer and electrolytic cells produced therefrom
US5463179A (en) * 1993-12-06 1995-10-31 Chaloner-Gill; Benjamin Solid electrolyte obtained by the polymerization of diacrylate monomer having a rigid alkane segment
US5482795A (en) * 1994-05-25 1996-01-09 Chaloner-Gill; Benjamin Solid electrolyte utilizing a polymeric matrix obtained by the polymerization of a substituted allylic chloroformate
US5514490A (en) * 1994-08-30 1996-05-07 Industrial Technology Research Institute Secondary lithium battery using a new layered anode material
JPH08153541A (en) * 1994-11-28 1996-06-11 Mitsubishi Cable Ind Ltd Lithium secondary battery
US5721070A (en) * 1995-04-13 1998-02-24 Shackle; Dale R. Alkali metal ion battery electrode material
CA2175856C (en) * 1995-05-18 2000-01-18 Hajime Arai A method for producing positive electrode material and lithium batteries incorporating this material
US5643695A (en) * 1995-09-26 1997-07-01 Valence Technology, Inc. Carbonaceous electrode and compatible electrolyte
US5660948A (en) * 1995-09-26 1997-08-26 Valence Technology, Inc. Lithium ion electrochemical cell
US5712059A (en) * 1995-09-26 1998-01-27 Valence Technology, Inc. Carbonaceous electrode and compatible electrolyte solvent
JP3460407B2 (en) * 1995-09-27 2003-10-27 ソニー株式会社 Non-aqueous electrolyte secondary battery
JP3523397B2 (en) 1995-11-07 2004-04-26 日本電信電話株式会社 Non-aqueous electrolyte secondary battery
JP3484003B2 (en) 1995-11-07 2004-01-06 日本電信電話株式会社 Non-aqueous electrolyte secondary battery
CN1147954C (en) * 1995-11-15 2004-04-28 旭化成电子材料元件株式会社 Composite polymer solid electrolyte and nonaqueous electrochemical device
EP1124158A1 (en) * 1996-02-26 2001-08-16 Matsushita Electric Industrial Co., Ltd. Pattern forming material and pattern forming method
US5700298A (en) * 1996-03-15 1997-12-23 Valence Technology, Inc. Carbon anode for lithium ion electrochemical cell
US6514640B1 (en) * 1996-04-23 2003-02-04 Board Of Regents, The University Of Texas System Cathode materials for secondary (rechargeable) lithium batteries
US5910382A (en) * 1996-04-23 1999-06-08 Board Of Regents, University Of Texas Systems Cathode materials for secondary (rechargeable) lithium batteries
US6103419A (en) * 1996-09-06 2000-08-15 Valence Technology, Inc. Solid secondary lithium cell based on lithiated zirconium, titanium or hafnium oxide cathode material
US5871866A (en) * 1996-09-23 1999-02-16 Valence Technology, Inc. Lithium-containing phosphates, method of preparation, and use thereof
US6447951B1 (en) * 1996-09-23 2002-09-10 Valence Technology, Inc. Lithium based phosphates, method of preparation, and uses thereof
US5851504A (en) * 1996-09-23 1998-12-22 Valence Technology, Inc. Carbon based electrodes
US6203946B1 (en) * 1998-12-03 2001-03-20 Valence Technology, Inc. Lithium-containing phosphates, method of preparation, and uses thereof
US5869207A (en) * 1996-12-09 1999-02-09 Valence Technology, Inc. Stabilized electrochemical cell
US6183718B1 (en) * 1996-12-09 2001-02-06 Valence Technology, Inc. Method of making stabilized electrochemical cell active material of lithium manganese oxide
JP4831588B2 (en) * 1997-01-17 2011-12-07 バシウム・カナダ・インコーポレーテッド Electrochemical generator
US6096234A (en) * 1997-01-23 2000-08-01 Shin-Etsu Chemical Co., Ltd. Cross-linked polymer solid electrolyte, method of manufacturing cross-linked solid polymer electrolyte, composite solid electrolyte, and thin solid cell employing composite solid electrolyte
US5830602A (en) * 1997-02-20 1998-11-03 Valence Technology, Inc. Carbonaceous active material and method of making same
CA2200998A1 (en) 1997-03-25 1998-09-25 Hydro-Quebec New lithium insertion electrode materials based on tetraoxyanions derivatives with olivine structure
US5908716A (en) * 1997-04-15 1999-06-01 Valence Technology, Inc. Lithium--containing sulfates, method of preparation and uses thereof
US6268088B1 (en) * 1997-05-15 2001-07-31 Cheil Industries Gel polymer electrolyte of vinyl acetate
CN1203462A (en) * 1997-06-20 1998-12-30 索尼株式会社 Cell
CA2215849A1 (en) * 1997-09-11 1999-03-11 Christophe Michot New solvent and electrolytic composition with high conductivity and wide stability range
US6077897A (en) * 1997-12-01 2000-06-20 Wen; Ten-Chin Polymeric composite electrolyte and process for producing same
JP4005192B2 (en) * 1997-12-09 2007-11-07 第一工業製薬株式会社 Solid battery
US6235433B1 (en) * 1997-12-19 2001-05-22 Nec Corporation High molecular gel electrolyte and secondary battery using the same
US6020087A (en) * 1998-01-30 2000-02-01 Valence Technology, Inc. Polymer electrolytes containing lithiated fillers
US6306215B1 (en) * 1998-03-10 2001-10-23 Valence Technology, Inc. Apparatus for coating current collectors
JP3932653B2 (en) * 1998-03-10 2007-06-20 ソニー株式会社 Non-aqueous electrolyte secondary battery
TW431009B (en) * 1998-05-22 2001-04-21 Teijin Ltd Electrolytic-solution-supporting polymer film and secondary battery
US6136472A (en) * 1998-06-26 2000-10-24 Valence Technology, Inc. Lithium-containing silicon/phosphates, method of preparation, and uses thereof including as electrodes for a battery
US6110622A (en) * 1998-07-22 2000-08-29 Wilson Greatbatch Ltd. Chemically machined current collector design
JP3951039B2 (en) * 1998-09-22 2007-08-01 第一工業製薬株式会社 Solid electrolyte and method for producing the same
EP1094533A1 (en) 1999-04-06 2001-04-25 Sony Corporation Active material of positive plate, nonaqueous electrolyte secondary cell, method for producing active material of positive material
CA2270771A1 (en) 1999-04-30 2000-10-30 Hydro-Quebec New electrode materials with high surface conductivity
US6468695B1 (en) 1999-08-18 2002-10-22 Valence Technology Inc. Active material having extended cycle life
JP3504195B2 (en) * 1999-09-16 2004-03-08 日本電信電話株式会社 Lithium secondary battery positive electrode active material and lithium secondary battery
US20020039688A1 (en) * 1999-09-29 2002-04-04 Jeremy Barker Lactone solvents for electrochemical cells
JP2001110414A (en) * 1999-10-04 2001-04-20 Nippon Telegr & Teleph Corp <Ntt> Material for activating positive electrode of lithium secondary battery and the lithium secondary battery
US6528033B1 (en) * 2000-01-18 2003-03-04 Valence Technology, Inc. Method of making lithium-containing materials
US7001690B2 (en) * 2000-01-18 2006-02-21 Valence Technology, Inc. Lithium-based active materials and preparation thereof
US6627337B2 (en) * 2000-02-16 2003-09-30 Wilson Greatbatch Ltd. Conversion of low rate energy into high rate energy by parallel discharging
JP3952491B2 (en) * 2000-04-24 2007-08-01 株式会社ジーエス・ユアサコーポレーション Electrode material and battery using the same
CA2796903C (en) * 2000-04-25 2015-03-31 Sony Corporation Positive electrode active material and non-aqueous electrolyte cell
JP3959929B2 (en) * 2000-04-25 2007-08-15 ソニー株式会社 Positive electrode and non-aqueous electrolyte battery
US6964827B2 (en) * 2000-04-27 2005-11-15 Valence Technology, Inc. Alkali/transition metal halo- and hydroxy-phosphates and related electrode active materials
US6777132B2 (en) * 2000-04-27 2004-08-17 Valence Technology, Inc. Alkali/transition metal halo—and hydroxy-phosphates and related electrode active materials
US6387568B1 (en) * 2000-04-27 2002-05-14 Valence Technology, Inc. Lithium metal fluorophosphate materials and preparation thereof
US6645670B2 (en) * 2000-05-16 2003-11-11 Wilson Greatbatch Ltd. Efficient cell stack for cells with double current collectors sandwich cathodes
JP2002042778A (en) * 2000-07-27 2002-02-08 Gs-Melcotec Co Ltd Battery manufacturing method and battery
CA2320661A1 (en) 2000-09-26 2002-03-26 Hydro-Quebec New process for synthesizing limpo4 materials with olivine structure
JP2002117908A (en) * 2000-10-06 2002-04-19 Sony Corp Nonaqueous electrolyte battery
JP4686852B2 (en) * 2000-12-04 2011-05-25 ソニー株式会社 Non-aqueous electrolyte battery
JP2002246025A (en) * 2001-02-22 2002-08-30 Mitsubishi Chemicals Corp Electrode active material for non-aqueous electrolyte secondary battery, and electrode and battery containing the same
KR100469163B1 (en) * 2001-03-26 2005-02-02 가부시끼가이샤 도시바 Anode-activating materials and non-aqueous electrolyte secondary cells
JP3615196B2 (en) * 2001-03-26 2005-01-26 株式会社東芝 Positive electrode active material and non-aqueous electrolyte secondary battery
KR100814540B1 (en) * 2001-04-06 2008-03-17 발렌스 테크놀로지, 인코포레이티드 Sodium Ion Batteries
JP2003157850A (en) * 2001-11-22 2003-05-30 Kyushu Univ Positive electrode material for secondary battery and secondary battery
JP4120860B2 (en) * 2001-11-22 2008-07-16 国立大学法人九州大学 Method for producing positive electrode material for secondary battery, and secondary battery
US7422823B2 (en) * 2002-04-03 2008-09-09 Valence Technology, Inc. Alkali-iron-cobalt phosphates and related electrode active materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6085015A (en) * 1997-03-25 2000-07-04 Hydro-Quebec Lithium insertion electrode materials based on orthosilicate derivatives
US6153333A (en) * 1999-03-23 2000-11-28 Valence Technology, Inc. Lithium-containing phosphate active materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP特开平11-25983A 1999.01.29

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10326164B2 (en) 2015-03-03 2019-06-18 Ut-Battelle, Llc High-conduction GE substituted LiAsS4 solid electrolyte

Also Published As

Publication number Publication date
US8318352B2 (en) 2012-11-27
KR101107423B1 (en) 2012-01-19
AU2003224801A1 (en) 2003-10-20
CA2479790C (en) 2012-06-26
WO2003085757A1 (en) 2003-10-16
EP1490917A4 (en) 2008-12-03
US20030190527A1 (en) 2003-10-09
KR20040111470A (en) 2004-12-31
JP4758610B2 (en) 2011-08-31
US20050181283A1 (en) 2005-08-18
JP2005522009A (en) 2005-07-21
EP1490917A1 (en) 2004-12-29
CN1650450A (en) 2005-08-03
CA2479790A1 (en) 2003-10-16

Similar Documents

Publication Publication Date Title
CN1650450B (en) Batteries comprising alkali-transition metal phosphates and preferred electrolytes
CN100372158C (en) Sodium ion batteries
US7422823B2 (en) Alkali-iron-cobalt phosphates and related electrode active materials
US7482097B2 (en) Alkali-transition metal phosphates having a +3 valence non-transition element and related electrode active materials
CN1795514B (en) Electrodes comprising mixed active particles
JP4965061B2 (en) Electrode active material for lithium battery, electrode for lithium battery and lithium battery
US20070141468A1 (en) Electrodes Comprising Mixed Active Particles
US20110052986A1 (en) Sodium Ion Batteries

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20100428

Termination date: 20150327

EXPY Termination of patent right or utility model